Multi-sensor gas sampling detection system for radical gases and short-lived molecules and method of use

ABSTRACT

The present application is directed to a multi-sensor gas sampling detection system and method for detecting and measuring the radicals in a radical gas stream and includes at least one radical gas generator in communication with at least one gas source. The radical gas generator may be configured to generate at least one radical gas stream which may be used within a processing chamber. As such, the processing chamber is in fluid communication with the radical gas generator. At least one analysis circuit in fluid communication with the radical gas generator may be used in the detection and measurement system. The analysis may be configured to receive a defined volume and/or flow rate of the radical gas stream. In one embodiment, the analysis circuit may be configured to react at least one reagent with radicals within the defined volume of the radical gas stream thereby forming at least one chemical species within at least one compound stream. At least one sensor module within the analysis circuit may be configured to measure a concentration of the chemical species within the compound stream. One or more flow measurement modules may be in fluid communication with the sensor module. During use, the flow measurement module may be configured to measure the volume of at least one of the compound stream and radical gas stream.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. Patent Application Ser.No. 62/593,721, filed on Dec. 1, 2017, entitled “Multi-Sensor GasSampling Detection System for Radical Gases and Short-Lived Moleculesand Method of Use,” and U.S. Patent Application Ser. No. 62/646,867,filed on Mar. 22, 2018, entitled “Multi-Sensor Gas Sampling DetectionSystem for Radical Gases and Short-Lived Molecules and Method of Use,”the contents both of which are hereby incorporated by reference in theirentirety herein.

BACKGROUND

Electronic devices and systems are being incorporated into anever-increasing number of device, systems, and applications. As aresult, market demand for low-cost integrated circuits having increasedcomplexity and diminished scale continues to grow. Variousmicrofabrication processes such as radical-based semiconductor waferprocesses have been developed to address scaling challenges. In order todesign and manufacture a high performance integrated circuitcost-effectively, the parameters of the radical-based semiconductorwafer manufacturing process need to be carefully controlled.

Presently, a number of radical-based semiconductor wafer processingmethods are in use. The radical gases used in the processes includeatoms, excited molecules as well as many short-lived molecules that donot normally exist in a gas, such as H, O, N, F, CI, Br, NH, NH₂, NF,CH, CH₂, COF, etc. While presently available radical-based semiconductorwafer processes have proven somewhat useful in the past a number ofshortcomings have been identified. For example, the radical speciesgenerated during wafer processing are short-lived thereby makingaccurate measurement and analysis challenging. As a result, rather thanrelying on quantitative analysis, presently available radical-basedsemiconductor wafer manufacturing methodologies involve preciseformulations and virtual metrology to achieve the desired waferarchitecture. Any variation in the formulations and/or control processesmay greatly affect production yield. In addition, the highly reactiveradical species generated during wafer processing tend to quicklydegrade analyzing devices and sensors, optical windows and components,and other systems or devices positioned within the radical stream orprocessing chamber.

Thus, in light of the foregoing, there is an ongoing need for amulti-sensor gas sampling detection system useful in radical-basedsemiconductor wafer processing.

SUMMARY

The present application is directed to a multi-sensor gas samplingdetection system and method for detecting and measuring atomic radicals,molecular radicals, and/or short-lived molecules in a radical gas streamor similar gas stream. The detecting and measuring system may include atleast one radical gas generator in communication with at least one gassource. The radical gas generator may be configured to generate at leastone radical gas stream which may be used within a processing chamber. Assuch, the processing chamber is in fluid communication with the radicalgas generator. At least one analysis circuit may be in fluidcommunication with the radical gas radical gas generator may be used inthe detection and measurement system. The analysis circuit may beconfigured to receive a defined volume and/or flow rate of the radicalgas stream. In one embodiment, the analysis circuit may be configured toreact at least one reagent with the radical gases within the definedvolume of the radical gas stream. The reaction produces at least onecompound stream (or reaction products) from the radical gases and the atleast one reagent, which may be in the form of a chemical species,charged particles, photon emission, or a thermal energy release, whichmay be measured by at least one sensor module within the analysiscircuit. One or more flow measurement modules may be in fluidcommunication with the sensor module. During use, the flow measurementmodule may be configured to measure the volume and/or flow rate of atleast one of the compound stream and radical gas stream. Based on theamount of reaction products measured and the volume and/or flow rate ofthe compound stream and the radical gas stream, the concentration or theamount of radical gases in the radical gas stream can be obtained.

The present application further discloses a method of measuring radicalgases in a radical gas stream. More specifically, the method formeasuring radicals in a gas stream includes providing at least oneradical gas stream having radicals therein. A sampling gas stream may becreated by directing a defined volume and/or flow rate of the radicalgas stream to at least one sampling module. At least one reagent may becombined with the radicals within the sampling gas stream to form atleast one compound stream having at least one chemical species therein.Thereafter, the concentration of the chemical species within thecompound stream may be measured using at least one sensor module.Further, the remaining volume of the radical gas stream may be directedinto at least one processing chamber. The flow rate of the radical gasstream and/or the compound gas stream may be measured using at least oneflow measurement module in fluid communication with the sensor module.Finally, the concentration of radicals within the processing chamber maybe calculated by comparing a ratio of the concentration of chemicalspecies within the compound stream per defined volume of the radical gasstream forming the sampling gas stream to the remaining volume of theradical gas stream.

In another embodiment, the present application discloses a method ofmeasuring radicals in a radical gas stream. The method includesproviding at least one radical gas stream having radicals therein. Atleast one upstream gas stream may be formed by directing a definedvolume of the radical gas stream to at least one upstream samplingmodule while directing the remaining volume of the radical gas streaminto at least one processing chamber. At least one chamber sampling gasstream may be formed by directing a defined volume of the radical gasstream from the processing chamber to at least one chamber samplingmodule while a remaining volume of the radical gas stream within theprocessing chamber is exhausted therefrom thereby forming at least oneexhaust gas stream. At least one exhaust sampling gas stream may beformed by directing a defined volume and/or flow rate of the exhaust gasstream to at least one exhaust sampling module. Thereafter, at least onereagent may be reacted with the radicals in the radical gas streamswithin at least one of the upstream sampling module, the chambersampling module, and the exhaust sampling module to form at least one ofan upstream compound stream, a chamber compound stream, and an exhaustcompound stream at least one of which having at least one chemicalspecies therein. The quantity of chemical species within at least one ofthe upstream compound stream, chamber compound stream, and exhaustcompound stream compound stream may be measured and the concentration ofradicals within the processing chamber may be calculated by comparing aratio of the concentration of chemical species within at least one ofthe upstream compound stream, chamber compound stream, and exhaustcompound stream per defined volume of the radical gas stream forming theupstream sampling gas stream, chamber sampling gas stream, and exhaustsampling gas stream to the remaining volume of the radical gas stream.

In addition, the present application discloses a multi-sensor gasdetection system for use in a wafer processing system. The waferprocessing system includes an upstream sampling module in fluidcommunication with a radical gas stream emitted from at least one sourceof radical gas source. The upstream sampling module may be configured toreceive a controlled volume and/or flow rate of the radical gas streamfrom the radical gas source. At least one reagent is reacted with thecontrolled volume and/or flow rate of the radical gas stream to producean upstream compound stream. Further, at least one chamber samplingmodule may be in fluid communication with the at least one radical gasstream present within at least one processing chamber. The chambersampling module may be configured to receive a controlled volume and/orflow rate of the radical gas stream and react with the controlled volumeand/or flow rate of the radical gas stream with at least one reagent toproduce a chamber compound stream. In addition, at least one exhaustsampling module may be in fluid communication with the radical gasstream exhausted from the processing chamber. The exhaust samplingmodule may be configured to receive a controlled volume and/or flow rateof the radical gas stream and react with the controlled volume of theradical gas stream with at least one reagent to produce an exhaustcompound stream. At least one sensor module may be communication with atleast one of the upstream sampling module, chamber sampling module, andexhaust sampling module. The sensor module may be configured to measurethe concentration of at least one of the upstream compound stream,chamber compound stream, and exhaust compound stream. At least one flowmodule may be in communication with at least one of the upstreamsampling module, chamber sampling module, exhaust sampling module, andsensor module. The flow module may be configured to control the flowrate of at least one of the upstream compound stream, chamber compoundstream, and exhaust compound stream.

The present application also discloses a sampling reaction module foruse in a reactive gas processing system. The sampling reaction modulemay include at least one analysis fixture having an analysis fixturebody. The analysis fixture body defines at least one fluid channeltherein. At least one fluid inlet port and fluid outlet port may beformed in the analysis fixture body. The inlet port and outlet port maybe in fluid communication with the fluid channel formed in the analysisfixture body. At least one coupling body extends from the analysisfixture body. In one embodiment, the coupling body includes at least onecoupling passage formed therein. At least one sampling tube traversingthrough the analysis fixture body may be positioned within the couplingpassage of the coupling body. Further, at least one module body definingat least one vacuum passage therein configured to receive at least oneanalysis fixture body thereon may be included in the sampling reactionmodule. The module body may have at least one sampling tube receiverformed therein such that the sampling tube receiver may be in fluidcommunication with the vacuum passage.

Lastly, the present application further discloses a calorimetry system.More specifically, the calorimetry system includes at least one reactivegas conduit defining at least one gas passage therein. During use, thegas passage is configured to have at least one reactive gas flowedtherethrough. Further, at least a first sensor body may be positionedwithin the gas passage of the reactive gas conduit. In one embodiment,the sensor body is configured to measure a temperature of the reactivegas flowed through the gas passage. In addition, at least one sensordevice may be in communication with the sensor body. During use, the atsensor device may be configured to receive temperature data relating tothe reactive gas flow from the sensor body. At least one processor maybe in communication with the first sensor device and may be configuredto calculate a sample power of the reactive gas flowing through thereactive gas conduit.

Other features and advantages of the multi-sensor gas sampling detectionsystem and method for detecting and measuring the radicals in a radicalgas stream as described herein will become more apparent from aconsideration of the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel aspects of the multi-sensor gas sampling detection system andmethod for detecting and measuring the radicals in a radical gas streamas disclosed herein will be more apparent by review of the followingfigures, wherein:

FIG. 1 shows a schematic diagram of an embodiment of a multi-sensor gassampling detection system;

FIG. 2 shows a schematic diagram of another embodiment of a multi-sensorgas sampling detection system wherein gas samples are taken from aradical gas stream upstream from a processing chamber and from withinthe processing chamber;

FIG. 3 shows a schematic diagram of another embodiment of a multi-sensorgas sampling detection system wherein gas samples are taken from aradical gas stream upstream from a processing chamber, from within theprocessing chamber, and downstream of the processing chamber;

FIG. 4 shows a schematic diagram of an alternate embodiment of amulti-sensor gas sampling detection system;

FIG. 5 shows a schematic diagram of an alternate embodiment of amulti-sensor gas sampling detection system having a reagent sourcecoupled thereto;

FIG. 6 shows a schematic diagram of another alternate embodiment of amulti-sensor gas sampling detection system;

FIG. 7 shows a schematic diagram of another alternate embodiment of amulti-sensor gas sampling detection system;

FIG. 8 shows an elevated perspective view of an embodiment of a samplingreaction module for use in a multi-sensor gas sampling detection system;

FIG. 9 shows an alternate elevated perspective view of an embodiment ofthe sampling reaction module for use in a multi-sensor gas samplingdetection system shown in FIG. 1;

FIG. 10 shows an elevated frontal perspective view of an embodiment ofan analysis fixture used with the sampling reaction module shown in FIG.1;

FIG. 11 shows an elevated frontal exploded view of the embodiment of ananalysis fixture used with the sampling reaction module shown in FIG. 1;

FIG. 12 shows an elevated posterior perspective view of an embodiment ofan analysis fixture used with the sampling reaction module shown in FIG.1;

FIG. 13 shows an elevated posterior exploded view of the embodiment ofan analysis fixture used with the sampling reaction module shown in FIG.1;

FIG. 14 shows an elevated perspective view of an embodiment of asampling reaction module body;

FIG. 15 shows an elevated cross-sectional perspective view of anembodiment of the sampling reaction module body shown in FIG. 14 viewedalong the line 15-15;

FIG. 16 shows a flow diagram describing a method of using themulti-sensor gas sampling detection system described in FIGS. 1-7;

FIG. 17 shows a flow diagram describing a method of using themulti-sensor gas sampling detection system described in FIGS. 1-7;

FIG. 18 shows a flow diagram describing an alternate method of using themulti-sensor gas sampling detection system described in FIGS. 1-7;

FIG. 19 shows a flow diagram describing an another method of using themulti-sensor gas sampling detection system described in FIGS. 1-7;

FIG. 20 shows graphically the method of using the multi-sensor gassampling detection system described in FIG. 19 to establish the upperbound limit and lower bound limit;

FIG. 21 shows a flow diagram describing a method of calibrating themulti-sensor gas sampling detection system described in FIGS. 1-7;

FIG. 22 shows graphically the extrapolated power measurements calculatedwhile calibrating the multi-sensor gas sampling detection systemdescribed in FIG. 21;

FIG. 23 shows graphically the measured concentration of oxygen radicalmeasured using an optical-based measurement system with the multi-sensorgas sampling detection system described in the present application;

FIG. 24 shows a flow diagram describing an optical-based method of usingthe multi-sensor gas sampling detection system described in FIGS. 1-7;

FIG. 25 shows a flow diagram describing a semiconductor-based method ofusing the multi-sensor gas sampling detection system described in FIGS.1-7;

FIG. 26 shows graphically the result of resistance change as the radicaloutput stream is activated and deactivated when using theresistance-based sampling architecture shown in FIG. 25,

FIG. 27 shows a schematic diagram of another alternate embodiment of amulti-sensor gas sampling detection system;

FIG. 28 shows an elevated perspective view of an embodiment of areactive gas conduit having at least one sensor body positioned withinthe reactive gas conduit for use in the embodiment of the gas samplingdetection system shown in FIG. 27;

FIG. 29 shows an elevated perspective view of another embodiment of areactive gas conduit having at least one sensor body positioned withinthe reactive gas conduit for use in the embodiment of the gas samplingdetection system shown in FIG. 27;

FIG. 30 shows an elevated perspective view of another embodiment of areactive gas conduit having at least one sensor body positioned withinthe reactive gas conduit for use in the embodiment of the gas samplingdetection system shown in FIG. 27;

FIG. 31 shows a flow diagram describing a method of using themulti-sensor gas sampling detection system described in FIGS. 27, 29,and 30;

FIG. 32 shows a flow diagram describing another method of using themulti-sensor gas sampling detection system described in FIGS. 27, 29,and 30;

FIG. 33 shows graphically the temperature delta of sensors bodiespositioned within the reactive gas conduit of the multi-sensor gassampling detection system described in FIGS. 27-30;

FIG. 34A shows graphically the performance of a first radical gasgenerator used in the embodiment of the sensor gas sampling detectionsystem described in FIGS. 27 and 30; and

FIG. 34B shows graphically the performance of a second radical gasgenerator used in the embodiment of the sensor gas sampling detectionsystem described in FIGS. 27 and 30.

DETAILED DESCRIPTION

The present application is directed to a multi-sensor gas samplingdetection system for atomic radicals, molecular radicals, andshort-lived molecules (hereinafter radicals) and method of use. Morespecifically, the present application discloses a gas sampling detectionsystem configured to permit the user to easily and accurately measurethe concentration of radicals in a gas stream. In one embodiment the gassampling detection system disclosed herein may be configured to measurethe concentration of radicals within a gas stream before introducing thegas stream into a processing chamber or similar vessel. In anotherembodiment, the gas sampling detection system disclosed herein may beconfigured to measure the concentration of radicals within a gas streamwithin the processing chamber or vessel. Optionally, the gas samplingdetection systems disclosed herein may be used to measure theconcentration of radicals within an exhaust stream, the exhaust streambeing evacuated from the processing chamber or vessel. Morespecifically, the methods disclosed herein allow for measurement of theconcentration of heretofore difficult-to-measure radicals by reactingthe radicals within a gas sample with selected elements and compounds tocreate chemical species which can be easily and accurately detected andmeasured using a variety of measuring techniques. In some embodiments,the measurement process may be conducted in situ. Optionally, themeasurement process may be conducted at a remote location.

FIG. 1 shows schematically an embodiment of a gas sampling detectionsystem useful for detecting the concentration of radicals within a gasstream. As shown, the gas sampling detection system 10 includes at leastone plasma generator and/or radical gas generator 12 in fluidcommunication with at least one processing chamber 16 via at least onegas passage 14. In one embodiment, the radical gas generator 12 mayinclude or may be in communication with at least one sample gas sourceand at least one plasma source. During use, the radical gas generator 12may be configured to energize and dissociate sample gases and generateat least one reactive gas stream. In one specific embodiment the radicalgas generator 12 comprises a RF toroidal plasma source, although thoseskilled in the art will appreciate that any variety of plasma sources orradical gas sources may be used with the present systems. In oneembodiment the radical gas generator 12 uses hydrogen (H₂) plasma tocreate atomic hydrogen. In another embodiment the radical gas generator12 utilizes oxygen (O₂) plasma to create atomic oxygen. Optionally, theradical gas generator 12 may utilize nitrogen trifluoride (NF₃),fluorine (F₂), chlorine (Cl₂) or any variety of other materials tocreate a reactive plasma containing one or more radicals within the gasstream. Alternatively, radical gases may be generated by other gasexcitation methods, including electron beam excitation, laserexcitation, or hot-filament excitation. Further, the above descriptiondiscloses various embodiments of RF-based plasma generation systems;although those skilled in the art will appreciate that any variety ofalternate radical gas generation systems may be used with the presentsystem. Exemplary alternate radical gas generation systems include,without limitation, glow discharge plasma systems, capacitively coupledplasma systems, cascade art plasma systems, inductively coupled plasmasystems, wave heated plasma systems, arc discharge plasma systems,coronal discharge plasma systems, dielectric barrier discharge systems,capacitive discharge systems, Piezoelectric direct discharge plasmasystems, and the like.

Referring again to FIG. 1, at least one processing chamber 16 may be influid communication with the radical gas generator 12 via at least onereactive gas conduit 14. In some applications, the reactive gas conduit14 is manufactured from a chemically inert material or a material havinglow chemical reactivity. Exemplary materials include, withoutlimitation, quartz, sapphire, stainless steel, strengthened steel,aluminum, ceramic materials, glass, brass, nickel, Y₂O₃, YAlO_(x),various alloys, and coated metals such as anodized aluminum. In oneembodiment a single reactive gas conduit 14 is in fluid communicationwith a single radical gas generator 12. In another embodiment multiplereactive gas conduits 14 are in fluid communication with a singlereactive gas generator 12. In yet another embodiment a single reactivegas conduit 14 is in communication with multiple radical gas generators12. As such, any number of reactive gas conduits 14 may be incommunication with any number of radical gas generators 12. Optionally,the reactive gas conduit 14 may include one or more valve devices orsystems, sensors, or similar devices 22 coupled thereto or incommunication there with. For example, one or more valve devices 22 maybe coupled to the reactive gas conduit 14 thereby permitting a user toselectively permit and/or restrict the flow of at least one reactive gasstream through the reactive gas conduit 14.

As shown in FIG. 1, the processing chamber 16 may be coupled to or incommunication with the radical gas generator 12 via the reactive gasconduit 14. In one embodiment, the processing chamber 16 comprises oneor more vacuum chambers or vessels configured to have one or moresubstrates, semiconductor wafers, or similar materials positionedtherein. For example, the processing chamber 16 may be used for atomiclayer processing of semiconductor substrates or wafers. Optionally, theprocessing chamber 16 may be used for processing any variety ofsubstrates or materials using any variety of processing methods and/orsystems. Exemplary processing methods include, without limitation,physical vapor deposition (PVD), chemical vapor deposition (CVD), rapidthermal chemical vapor deposition (RTCVD), atomic layer deposition(ALD), atomic layer etching (ALE), and the like. Those skilled in theart will appreciate that the processing chamber 16 be manufactured fromany variety of materials, including, without limitation, stainlesssteel, aluminum, mild steel, brass, high-density ceramics, glass,acrylic, and the like. For example, at least one interior surface of theprocessing chamber 16 may include at least one coating, anodizedmaterial, sacrificial material, physical feature or element, and thelike intended to selectively vary the reactivity, durability, and/orfill micro-pores on the interior surfaces of the processing chamber 16.At least one exhaust conduit 18 may be coupled to the processing chamber16 and configured to evacuate one or more gases or materials from theprocessing chamber 16. Optionally, one or more control sensors, valves,scrubbers, or similar devices 24 may be coupled to or positionedproximate to the exhaust conduit 18, thereby permitting the user toselectively evacuate one or more gases or other materials from theprocessing chamber 16.

Referring again to FIG. 1, at least one chamber processor module 20 maybe coupled to or otherwise in communication with the processing chamber16 and/or various components of the processing system. The chamberprocessing module 20 may be configured to provide localized control ofthe various components forming the processing system 10. In theillustrated embodiment the chamber processing module 20 is incommunication with the processing chamber 16 via a conduit, althoughthose skilled in your will appreciate that the chamber processing module20 may communicate with any of the components forming the processingsystem 10 via conduit, wirelessly, or both.

As shown in FIG. 1, at least one sampling module 32 may be in fluidcommunication with the radical gas generator 12 via at least onesampling conduit 30. Those skilled in the art will appreciate that thesampling conduit 30 may be manufactured from any variety of materialsincluding, without limitations, stainless steel, alloys, aluminum,brass, ceramics materials, glass, polymers, plastics, carbon fibercarbon-based materials, graphite, silicon, silicon dioxide, siliconcarbide, and the like. As such, in some embodiments the sampling conduit30 may be configured to chemically react with the highly reactive atomicradicals, molecular radicals, and short-lived molecules contained withinthe radical gas stream flowing therein. In yet another embodiment, thesampling conduit 30 may consist of a catalytic material to facilitatethe recombination of atomic gas species into its molecular gas species,such that the recombination energy of the atomic gas is released andmeasured. In other embodiments, the sampling conduit 30 may beconfigured to be chemically inert. Optionally, the sampling conduit 30may include any variety of sensors, valves, heating elements, coolingelements, and the like thereon. In one embodiment, the sampling conduit30 is coupled directly to and in fluid communication with the radicalgas generator 12. In the illustrated embodiment the sampling conduit 30is in fluid communication with the radical gas generator 12 via thereactive gas conduit 14. Optionally, the sampling conduit 30 may be influid communication with the sampling control valve 22 positioned on thereactive gas conduit 14. For example, the sampling control valve 22 maybe configured to selectively direct a prescribed volume of reactive gastraversing through the reactive gas conduit 14 to the sampling module 32via the sampling conduit 30. In another embodiment, the sampling controlvalve 22 may be configured to selectively direct a prescribed flow rateof reactive gas traversing through the reactive gas conduit 14 to thesampling module 32 via the sampling conduit 30. Further, any number ofadditional components, valves, sensors, and the like may be positionedanywhere along the sampling conduit 30. For example, in the illustratedembodiment at least one sensor and/or control device 50 may bepositioned along the sampling conduit 30. Exemplary sensor devicesinclude, without limitations, thermocouples, temperature sensors,optical sensors, UV, optical or infrared spectrometers, charge particledetectors, vacuum gauges, mass spectrometers, and the like. For example,in one embodiment the sensor device 50 comprises at least onethermistor. In another embodiment the sensor device 50 comprises atleast one calorimetry system or device. An embodiment of a novelcalorimetry system is discussed in detail and shown in FIGS. 8-15 of thepresent application. Optionally, the sensor device 50 may comprise oneor more titration systems or devices. Those skilled in the arts willappreciate the sensor device 50 may comprise any number of in situmeasuring devices were systems, flow valves, flowmeters, flow verifiers,and the like.

Referring again to FIG. 1, in the illustrated embodiment the samplingmodule 32 is coupled to at least one molecular compound stream conduit34. Like the sampling conduit 30 the molecular compound stream conduit34 may be manufactured from any variety of materials including, withoutlimitation, graphite, silica, carbon fiber, silicon dioxide, silica andcarbide, carbon-based materials, silica-based materials, stainlesssteel, alloys, aluminum, brass, ceramics materials, glass, polymers,plastics, and the like. In one embodiment at least a portion of at leastone of the sampling conduit 30 and/or the molecular compound streamconduit 34 may be configured to react with the radical gas streamflowing therein. For example, one embodiment at least a portion of thesampling conduit 30 and/or molecular compound stream conduit 34 may beconfigured to react with radicals within the gas flow to form chemicalspecies more stable and capable of accurate measurement as compared tothe radicals within the radical gas stream.

As shown in FIG. 1, at least one sensor module 36 is in fluidcommunication with the sampling module 32 via the molecular compoundstream conduit 34. In one embodiment, the sensor module 36 may beconfigured to detect and measure the concentration of radicals in atleast one gas flow. Any variety of devices or systems may be used withinor to form the sensor module 36. For example, in one embodiment thesensor module 36 comprises at least one detector configured to measurethe radical flux within the radical gas stream. In another embodiment,the sensor module 36 is configured to measure the concentration of atleast one chemical species within a gas flow. For example, the sensormodule 36 may be configured to measure the concentration for carbonmonoxide (CO), carbon dioxide (CO₂), carbon-hydrogen molecules(methylidyne radical), methylene (CH₂), methyl-group compounds (CH₃),methane (CH₄), silicon tetrafluoride, and similar compounds. In onespecific embodiment the sensor module 36 includes at least one opticalgas imaging camera or device such as Fourier Transform Infraredspectroscopy system (hereinafter FTIR system), tunable filterspectroscopy system (hereinafter TFS system), mass spectrography,optical absorption spectroscopy and the like. Optionally, the sensingmodule 36 may further include at least one titration system or device.In one embodiment, in one embodiment, the sensing module 36 may beconfigured to reduce or eliminate recombination of the radicals withinthe gas stream into its molecular species. In another embodiment, thesensor module 36 may be configured to permit recombination of theradicals within a gas stream to its molecular species.

Referring again to FIG. 1, at least one sensor module output conduit 38is in fluid communication with the sensor module 36 and the flowmeasurement and/or flow control module 40. In some embodiments, the flowmeasurement module 40 is configured to accurately measure a portion ofthe gas stream flowing there through. For example, the flow of the gasstream may be measured using a mass flow verifier (MFV). In anotherembodiment, the flow of the gas stream may be measured using a mass flowmeter (MFM). Optionally, the flow may be determined by measuring thepressure differential between an orifice of known size within themulti-sensor gas sampling detection system 10 with the fluidconductance. Those skilled in the art will appreciate that any varietyof flow measuring devices or systems they be used with the gas samplingdetection system 10 disclosed herein. As shown in FIG. 1, at least oneexhaust conduit 42 may be coupled to or in communication with the flowmeasurement module 40 and configured to exhaust the radical gas streamfrom the gas sampling detection system 10. Optionally, the exhaustconduit 42 may be in fluid communication with at least one vacuum source(not shown).

As shown in FIG. 1, the processing system 10 may include at least oneoptional processor module 52 which may be in communication with at leastone component of the processing system 10. For example, in theillustrated embodiment, an optional processor module 52 is incommunication with the radical gas generator 12 via at least oneprocessor conduit 54. Further, the optional processor system 52 may bein communication with at least one of the optional sensor 50 via theprocessor conduit 54 and at least one optional sensor conduit 56, thesampling module 32 via the processor conduit 54 and at least onesampling conduit 58, the sensor module 36 via at least one sensor moduleconduit 60, and the flow measurement module 40 via at least one flowmeasurement conduit 62. In one embodiment, the optional processor module52 may be configured to provide and receive data from at least one ofthe radical gas generator 12, the optional sensor 50, the samplingmodule 32, the sensor module 36, and the flow measurement module 40. Assuch, the optional processor module 52 may be configured to measure theflow condition within the processing system 10 and selectively vary theoperating conditions of the processing system 10 to optimize systemperformance. More specifically, the optional processor module 52 may beconfigured to measure the concentration of radicals within the gasstream and vary the operating characteristics of the radical gasgenerator 12 to increase or decrease the concentration of radicalswithin the radical gas stream. Further, the optional processor module 52may be in communication with and provide/receive data from at least oneof the optional valve device 22, sensor 24, and chamber processor module20 via at least one optional processing conduit 64. Optionally, theoptional processor module 52 may be in communication with the variouscomponents of the processing system 10 wirelessly. Further, the optionalprocessor module 52 may be configured to store performance data,processing formulas and times, lot number, and the like. In addition,the optional processor module 52 may be configured to communicate withone or more external processors via at least one computer network.

Optionally, as shown in FIG. 1, at least one analysis system or circuit66 may be formed within the processing system 10. As shown, the analysissystem 66 may include at least one of the sampling module 32, sensormodule 36, flow measurement module 49, optional sensor 50, optionalprocessor module 52, and the like. Further, the analysis system 66 mayfurther include valve device 22 or other devices and components withinthe processing system 10.

FIG. 2 shows schematically another embodiment of a gas samplingdetection system useful for detecting the concentration of radicalswithin a gas stream. The various components of the processing system 110shown in FIG. 2 perform comparably to similarly named components shownin FIG. 1. Like the previous embodiment, the gas sampling detectionsystem 110 may include at least one radical gas generator and/orreactive gas generator 112 configured to provide a reactive gas streamhaving radicals therein. The radical gas generator 112 may be in fluidcommunication with at least one processing chamber 116 via at least onegas passage 114. Like the previous embodiment, the radical gas generator112 is in communication with at least one sample gas source and at leastone plasma source configured to energize and dissociate sample gases andgenerate at least one reactive gas stream in response thereto.

Referring again to FIG. 2, optionally, the reactive gas conduit 114 mayinclude one or more valve devices or systems, sensors, or similardevices 122 coupled thereto or in communication there with. For example,one or more valve devices 122 may be coupled to or otherwise incommunication with the reactive gas conduit 114 thereby permitting auser to selectively permit and/or restrict the flow of at least onereactive gas stream through the reactive gas conduit 114. In oneembodiment, the valve device 122 may be in communication with at leastone optional processing module 152 via at least one processor conduit154. Optionally, the processing module 152 may be configured tocommunicate with the various components of the processing system 110wirelessly. During use, the processor module 152 may be configured toselectively open and/or close the valve device 122 thereby permitting orrestrict the flow of the radical gas stream generated by the radical gasgenerator 112 into the sampling module 132.

As shown in FIG. 2, at least one processing chamber 116 may be coupledto or in communication with the radical gas generator 112 via thereactive gas conduit 114. At least one exhaust conduit 118 may becoupled to the processing chamber 116 and configured to evacuate one ormore gases or materials from the processing chamber 116. Optionally, oneor more control sensors, valves, scrubbers, or similar devices 124 maybe coupled to or positioned proximate to the exhaust conduit 118,thereby permitting the user to selectively evacuate one or more gases orother materials from the processing chamber 116.

Referring again to FIG. 2, like the previous embodiment, at least onechamber processor module 120 may be coupled to or otherwise incommunication with the processing chamber 118 and/or various componentsof the processing system. The chamber processing module 120 may beconfigured to provide localized control of the various componentsforming the processing system 110. In the illustrated embodiment thechamber processing module 120 is in communication with the processingchamber 116 via a conduit, although those skilled in the art willappreciate that the chamber processing module 120 may communicate withany of the components forming the processing system 110 via a conduit,wirelessly, or both.

As shown in FIG. 2, at least one sampling module 132 may be in fluidcommunication with the radical gas generator 112 via at least onesampling conduit 130. Those skilled in the art will appreciate that thesampling conduit 130 may be manufactured from any variety of materialsincluding, without limitations, stainless steel, alloys, aluminum,brass, ceramics materials, glass, polymers, plastics, carbon fibercarbon-based materials, graphite, silicon, silicon dioxide, siliconcarbide, and the like. As such, the sampling conduit 130 may beconfigured to chemically react with the highly reactive radicalscontained within the radical gas stream flowing therein. In anotherembodiment, the sampling conduit 130 may be configured to be chemicallyinert. In one embodiment, the sampling conduit 130 is coupled directlyto and in fluid communication with the radical gas generator 112. In theillustrated embodiment the sampling conduit 130 is in fluidcommunication with the radical gas generator 112 via the reactive gasconduit 114. Optionally, the sampling conduit 130 may be in fluidcommunication with the sampling control valve 122 positioned on thereactive gas conduit 114. For example, the sampling control valve 122may be configured to selectively direct a prescribed volume of reactivegas traversing through the reactive gas conduit 114 to the samplingmodule 132 via the sampling conduit 130. Optionally, the samplingcontrol valve 122 may be configured to selectively direct a prescribedflow rate of reactive gas traversing through the reactive gas conduit114 to the sampling module 132 via the sampling conduit 130. Further,any number of additional components, valves, sensors, and the like maybe positioned anywhere along the sampling conduit 130. For example, inthe illustrated embodiment at least one sensor and/or control device 150may be positioned along the sampling conduit 130. Exemplary sensordevices include, without limitations, thermocouples, temperaturesensors, vacuum gauges, and the like. For example, in one embodiment thesensor device 150 comprises at least one thermistor. In anotherembodiment the sensor device 150 comprises at least one calorimetrysystem or device. Optionally, the sensor device 150 may comprise one ormore titration systems or devices. Those skilled in the art willappreciate that the sensor device 150 may comprise any number of in situmeasuring devices or systems, flow valves, flowmeters, flow verifiers,and the like.

Referring again to FIG. 2, the sampling module 132 may also be in fluidcommunication with the processing chamber 116 via at least one chambersample gas conduit 144. As such, the sampling module 132 may beconfigured to analyze the radical gas stream upstream of the processingchamber 116 and within the processing chamber 116. Such analysis mayoccur sequentially or simultaneously. Like the sampling conduit 130, thechamber sample gas conduit 144 may include one or more valves, sensors,and the like thereon. As such, the flow of sample gas from theprocessing chamber 116 to the sampling module 132 may be selectivelyvaried.

With reference to FIG. 2, the sampling module 132 may be coupled to atleast one molecular compound stream conduit 134. Like the samplingconduit 130 the molecular compound stream conduit 134 may bemanufactured from any variety of materials including, withoutlimitation, graphite, silica, carbon fiber, silicon dioxide, silica andcarbide, carbon-based materials, silica-based materials, stainlesssteel, alloys, aluminum, brass, ceramics materials, glass, polymers,plastics, and the like. In one embodiment at least a portion of at leastone of the sampling conduit 130 and/or the molecular compound streamconduit 134 may be configured to react with the radical gas streamflowing therein. For example, in one embodiment at least a portion ofthe sampling conduit 130 and/or molecular compound stream conduit 134may be configured to react with radicals within the gas flow to formchemical species more stable and capable of accurate measurement ascompared to the radicals contained within the radical gas stream.

As shown in FIG. 2, like the previous embodiment, at least one sensormodule 136 may be in fluid communication with the sampling module 132via the molecular compound stream conduit 134. Optionally, the sensormodule 136 may be configured to detect and measure the concentration ofradicals in at least one gas flow. Any variety of devices or systems maybe used within or to form the sensor module 136. For example, in oneembodiment the sensor module 136 comprises at least one detectorconfigured to measure the radical flux within the radical gas stream. Inanother embodiment, the sensor module 136 is configured to measure theconcentration of at least one chemical species within a gas flow. Forexample, the sensor module 136 may be configured to measure theconcentration for carbon monoxide (CO), carbon dioxide (CO₂),carbon-hydrogen molecules (methylidyne radical), methylene (CH₂),methyl-group compounds (CH₃), methane (CH₄), silicon tetrafluoride, andsimilar compounds. In one specific embodiment the sensor module 136includes at least one optical gas imaging camera or device such asFourier Transform Infrared spectroscopy system (hereinafter FTIRsystem), tunable filter spectroscopy system (hereinafter TFS system),mass spectrography, optical absorption spectroscopy and the like.Optionally, the sensing module 136 may further include at least onetitration system or device. In one embodiment, the sensing module 136may be configured to reduce or eliminate recombination of the radicalswithin the gas stream into its molecular species. In another embodimentthe sensor module 136 may be configured to permit recombination of theradicals within a gas stream to its molecular species.

Referring again to FIG. 2, at least one sensor module output conduit 138is in fluid communication with the sensor module 136 in the flowmeasurement and/or flow control module 140, which may be configured toaccurately measure a portion of the gas stream flowing there through.Like the previous embodiment, the flow of the gas stream may be measuredusing a mass flow verifier (MFV). In another embodiment, the flow of thegas stream may be measured using a mass flow meter (MFM). Optionally,the flow volume or rate may be determined by measuring the pressuredifferential between an orifice of known size within the multi-sensorgas sampling detection system 110 with the fluid conductance. Thoseskilled in the art appreciate that any variety of flow measuring devicesor systems can be used with the gas sampling detection system 110disclosed herein. As shown in FIG. 2, at least one exhaust conduit 142may be coupled to or in communication with the flow measurement module140 and configured to exhaust the radical gas stream from the gassampling detection system 110. Optionally, the exhaust conduit 142 maybe in fluid communication with at least one vacuum source (not shown).

As stated above, the processing system 110 may include at least oneoptional processor module 152 in communication with at least onecomponent of the processing system 110. For example, the optionalprocessor module 152 may be in communication with the radical gasgenerator 112 via at least one processor conduit 154. Further, theoptional processor system 152 may be in communication with the optionalsensor 150 via the processor conduit 154 and at least one optionalsensor conduit 156, the sampling module 132 via the processor conduit154 and at least one sampling conduit 158, the sensor module 136 via atleast one sensor module conduit 160, and the flow measurement module 140via at least one flow measurement conduit 162. In one embodiment, theoptional processor module 152 may be configured to provide and receivedata from at least one of the radical gas generator 112, the optionalsensor 150, the sampling module 132, the sensor module 136, and the flowmeasurement module 140. As such, the optional processor module 152 maybe configured to measure the flow conditions within the processingsystem 110 and selectively vary the operating conditions of theprocessing system 110 to optimize system performance. More specifically,the optional processor module 152 may be configured to measure theconcentration of radicals within the gas stream vary the operatingcharacteristics of the radical gas generator 112 to increase or decreasethe concentration of radicals within the radical gas stream. Further,the optional processor module 152 may be in communication with andprovide/receive data from at least one of the optional valve device 122,sensor 124, and chamber processor module 120 via at least one optionalprocessing conduit 164. Optionally, the processor module 152 may be incommunication with an external network.

Optionally, as shown in FIG. 2, like the previous embodiment, at leastone analysis system or circuit 166 may be formed within the processingsystem 110. As shown, the analysis system 166 may include at least oneof the sampling module 132, sensor module 136, flow measurement module149, optional sensor 150, optional processor module 152, and the like.Further, the analysis system 166 may further include the valve device122 or other devices and components within the processing system 110.

FIG. 3 shows schematically still another embodiment of a gas samplingdetection system useful for detecting the concentration of radicalswithin a gas stream. Like FIG. 2, the various components of theprocessing system 210 shown in FIG. 3 perform comparably to similarlynamed components shown in FIGS. 1 and 2. Like the previous embodiments,the gas sampling detection system 210 may include at least one radicalgas generator and/or reactive gas generator 212 configured to provide areactive gas stream having radicals therein. The radical gas generator212 may be in fluid communication with at least one processing chamber216 via at least one gas passage 214. Like the previous embodiment, theradical gas generator 212 is in communication with at least one samplegas source and at least one plasma source configured to energize anddissociate sample gases and generate at least one reactive gas stream inresponse thereto.

Referring again to FIG. 3, optionally, the reactive gas conduit 214 mayinclude one or more valve devices or systems, sensors, or similardevices 222 coupled thereto or in communication there with. For example,one or more valve devices 222 may be positioned within or coupled to thereactive gas conduit 214 thereby permitting a user to selectively permitand/or restrict the flow of at least one reactive gas stream through thereactive gas conduit 214.

As shown in FIG. 3, at least one processing chamber 216 may be coupledto or in communication with the radical gas generator 212 via thereactive gas conduit 214. At least one exhaust conduit 218 may becoupled to the processing chamber 216 and configured to evacuate one ormore gases or materials from the processing chamber 216. Optionally, oneor more control sensors, valves, scrubbers, or similar devices 224 maybe coupled to or positioned proximate to the exhaust conduit 218,thereby permitting the user to selectively evacuate one or more gases orother materials from the processing chamber 216.

Referring again to FIG. 3, like the previous embodiment, at least onechamber processor module 220 may be coupled to or otherwise incommunication with the processing chamber 218 and/or various componentsof the processing system. The chamber processing module 220 may beconfigured to provide localized control of the various componentsforming the processing system 210. In the illustrated embodiment thechamber processing module 220 is in communication with the processingchamber 216 via a conduit, although those skilled in the art willappreciate that the chamber processing module 220 may communicate withany of the components forming the processing system 210 via a conduit,wirelessly, or both.

As shown in FIG. 3, at least one sampling module 232 may be in fluidcommunication with the radical gas generator 212 via at least onesampling conduit 230. Those skilled in the art appreciate the samplingconduit 230 may be manufactured from any variety of materials including,without limitations, stainless steel, alloys, aluminum, brass, ceramicsmaterials, glass, polymers, plastics, carbon fiber carbon-basedmaterials, graphite, silicon, silicon dioxide, silicon carbide, and thelike. As such, the sampling conduit 230 may be configured to chemicallyreact with the highly reactive radicals contained within the radical gasstream flowing therein. In another embodiment, the sampling conduit 230may be configured to be chemically inert. In one embodiment, thesampling conduit 230 is coupled directly to and in fluid communicationwith the radical gas generator 212. In the illustrated embodiment thesampling conduit 230 is in fluid communication with the radical gasgenerator 212 via the reactive gas conduit 214. Optionally, the samplingconduit 230 may be in fluid communication with the sampling controlvalve 222 positioned on the reactive gas conduit 214. For example, thesampling control valve 222 may be configured to selectively direct aprescribed volume of reactive gas traversing through the reactive gasconduit 214 to the sampling module 232 via the sampling conduit 230.Optionally, the sampling control valve 222 may be configured toselectively direct a prescribed flow rate of reactive gas traversingthrough the reactive gas conduit 214 to the sampling module 232 via thesampling conduit 230. Further, any number of additional components,valves, sensors, and the like may be positioned anywhere along thesampling conduit 230. For example, in the illustrated embodiment atleast one sensor and/or control device 250 may be positioned along thesampling conduit 230. Exemplary sensor devices include, withoutlimitations, thermocouples, temperature sensors, vacuum gauges, and thelike. For example, in one embodiment the sensor device 250 comprises atleast one thermistor. In another embodiment the sensor device 250comprises at least one calorimetry system or device. Optionally, thesensor device 250 may comprise one or more titration systems or devices.Those skilled in the art appreciate the sensor device 250 may compriseany number of in situ measuring devices or systems, flow valves,flowmeters, flow verifiers, and the like.

Referring again to FIG. 3, the sampling module 232 may also be in fluidcommunication with the processing chamber 216 and the exhaust conduit218 via at least one of the at least one chamber sample gas conduit 244and/or sample exhaust conduit 246. As such, the sampling module 232 maybe configured to analyze the radical gas stream upstream of theprocessing chamber 216, the radical gas stream within the processingchamber 216, and the radical gas stream being emitted from theprocessing chamber via the exhaust conduit 218. Such analysis may occursequentially or simultaneously. Like the sampling conduit 230, thechamber sample gas conduit 244, and/or the exhaust conduit 218 mayinclude one or more valves, sensors, and the like thereon. As such, theflow of sample gas from the processing chamber 216 to the samplingmodule 232, and/or the flow of sample gas from the exhaust conduit 218to the sampling module 232, or both, may be selectively varied.

With reference to FIG. 3, the sampling module 232 may be coupled to atleast one molecular compound stream conduit 234. Like the samplingconduit 230, the molecular compound stream conduit 234 may bemanufactured from any variety of materials including, withoutlimitation, graphite, silica, carbon fiber, silicon dioxide, silica andcarbide, carbon-based materials, silica-based materials, stainlesssteel, alloys, aluminum, brass, ceramics materials, glass, polymers,plastics, and the like. In one embodiment, at least a portion of atleast one of the sampling conduit 230 and/or the molecular compoundstream conduit 234 may be configured to react with the radical gasstream flowing therein. For example, in one embodiment at least aportion of the sampling conduit 230 in/or molecular compound streamconduit 234 may be configured to react with radicals within the gas flowto form chemical species more stable and capable of accurate measurementas compared to the radicals container within the radical gas stream.

As shown in FIG. 3, like the previous embodiments, at least one sensormodule 236 is in fluid communication with the sampling module 232 viathe molecular compound stream conduit 234. Optionally, the sensor module236 may be configured to detect and measure the concentration ofradicals in at least one gas flow. Any variety of devices or systems maybe used within or to form the sensor module 236. For example, in oneembodiment the sensor module 236 comprises at least one detectorconfigured to measure the radical flux within the radical gas stream. Inanother embodiment, the sensor module 236 is configured to measure theconcentration of at least one chemical species within a gas flow. Forexample, the sensor module 236 may be configured to measure theconcentration of carbon monoxide (CO), carbon dioxide (CO₂),carbon-hydrogen molecules (methylidyne radical), methylene (CH₂),methyl-group compounds (CH₃), methane (CH₄), silicon tetrafluoride, andsimilar compounds. In one specific embodiment, the sensor module 236includes at least one optical gas imaging camera or device such asFourier Transform Infrared spectroscopy system (hereinafter FTIRsystem), tunable filter spectroscopy system (hereinafter TFS system),mass spectrography, optical absorption spectroscopy and the like.Optionally, the sensor module 236 may further include at least onetitration system or device. In one embodiment, in one embodiment, thesensor module 236 may be configured to reduce or eliminate recombinationof the radicals within the gas stream into its molecular species.Another embodiment the sensor module 236 may be configured to permitrecombination of the radicals within a gas stream to its molecularspecies.

Referring again to FIG. 3, at least one sensor module output conduit 238is in fluid communication with the sensor module 236 and the flowmeasurement and/or flow control module 240, which may be configured toaccurately measure a portion of the gas stream flowing there through.Like the previous embodiment, the flow of the gas stream may be measuredusing a mass flow verifier (MFV). In another embodiment, the flow of thegas stream may be measured using a mass flow meter (MFM). Optionally,the flow may be determined by measuring the pressure differentialbetween an orifice of known size within the multi-sensor gas samplingdetection system 210 with the fluid conductance. Those skilled in theart appreciate that any variety of flow measuring devices or systems maybe used with the gas sampling detection system 210 disclosed herein. Asshown in FIG. 3, at least one exhaust conduit 242 may be coupled to orin communication with the flow measurement module 240 and configured toexhaust the radical gas stream from the gas sampling detection system210. Optionally, the exhaust conduit 242 may be in fluid communicationwith at least one vacuum source (not shown).

As stated above, the processing system 210 may include at least oneoptional processor module 252 in communication with at least onecomponent of the processing system 210. For example, the optionalprocessor module 252 may be in communication with the radical gasgenerator 212 via at least one processor conduit 254. Further, theoptional processor system 252 may be in communication with at least oneof the optional sensor 250 via the processor conduit 254 and at leastone optional sensor conduit 256, the sampling module 232 via theprocessor conduit 254 and at least one sampling conduit 258, the sensormodule 236 via at least one sensor module conduit 260, and the flowmeasurement module 240 via at least one flow measurement conduit 262. Inone embodiment, the optional processor module 252 may be configured toprovide and receive data from at least one of the radical gas generator212, the optional sensor 250, the sampling module 232, the sensor module236, and the flow measurement module 240. As such, the optionalprocessor module 252 may be configured to measure the flow conditionwithin the processing system 210 and selectively vary the operatingconditions of the processing system 210 to optimize system performance.More specifically, the optional processor module 252 may be configuredto measure the concentration of radicals within the gas stream vary theoperating characteristics of the radical gas generator 212 to increaseor decrease the concentration of radicals within the radical gas stream.Further, the optional processor module 252 may be in communication withand provide/receive data from at least one of the optional valve device222, sensor 224, and chamber processor module 220 via at least oneoptional processing conduit 264. Further, the processor module 252 maybe in communication with an external network.

Optionally, as shown in FIG. 3, like the previous embodiments, at leastone analysis system or circuit 266 may be formed within the processingsystem 210. As shown, the analysis system 266 may include at least oneof the sampling module 232, sensor module 236, flow measurement module249, optional sensor 250, optional processor module 252, and the like.Further, the analysis system 266 may further include the valve device222 or other devices and components within the processing system 210.

FIG. 4 shows schematically another embodiment of a gas samplingdetection system useful for detecting the concentration of radicalswithin a gas stream. Unlike the previous embodiments, the presentembodiment includes multiple sampling modules providing data to one ormore sensor modules. Like the previous embodiments, the variouscomponents of the processing system 310 shown in FIG. 4 performcomparably to similarly named components shown in FIGS. 1-3. Like theprevious embodiments, the gas sampling detection system 310 may includeat least one radical gas generator and/or reactive gas generator 312configured to provide a reactive gas stream having radicals therein. Theradical gas generator 312 may be in fluid communication with at leastone processing chamber 316 via at least one gas passage 314. Optionally,the reactive gas conduit 314 may include one or more valve devices orsystems, sensors, or similar devices 322 coupled thereto or incommunication there with. For example, one or more valve devices 322 maybe positioned or coupled to the reactive gas conduit 314 therebypermitting a user to selectively permit and/or restrict the flow of atleast one reactive gas stream through the reactive gas conduit 314.

As shown in FIG. 4, at least one processing chamber 316 may be coupledto or in communication with the radical gas generator 312 via thereactive gas conduit 314. At least one exhaust conduit 318 may becoupled to the processing chamber 316 and configured to evacuate one ormore gases or materials from the processing chamber 316. Optionally, oneor more control sensors, valves, scrubbers, or similar devices 324 maybe coupled to or positioned proximate to the exhaust conduit 318,thereby permitting the user to selectively evacuate one or more gases orother materials from the processing chamber 316.

Referring again to FIG. 4, like the previous embodiments, at least onechamber processor module 320 may be coupled to or otherwise incommunication with the processing chamber 318 and/or various componentsof the processing system. The chamber processing module 320 may beconfigured to provide localized control over the various componentsforming the processing system 310. The illustrated embodiment thechamber processing module 320 is in communication with the processingchamber 316 via a conduit, although those skilled in the art appreciatethat the chamber processing module 320 may communicate with any of thecomponents forming the processing system 310 via a conduit, wirelessly,or both.

As shown in FIG. 4, at least one upstream sampling module 332 may be influid communication with the radical gas generator 312 via at least onesampling conduit 330. Those skilled in the art will appreciate that thesampling conduit 330 may be manufactured from any variety of materialsincluding, without limitations, stainless steel, alloys, aluminum,brass, ceramics materials, glass, polymers, plastics, carbon fibercarbon-based materials, graphite, silicon, silicon dioxide, siliconcarbide, and the like. As such, the sampling conduit 330 may beconfigured to chemically react with the highly reactive radicalscontained within the radical gas stream flowing therein. In anotherembodiment, the sampling conduit 330 may be configured to be chemicallyinert. In one embodiment, the sampling conduit 330 is coupled directlyto and in fluid communication with the radical gas generator 312. In theillustrated embodiment the sampling conduit 330 is in fluidcommunication with the radical gas generator 312 via the reactive gasconduit 314. Optionally, the sampling conduit 330 may be in fluidcommunication with the sampling control valve 322 positioned on thereactive gas conduit 314. For example, the sampling control valve 322may be configured to selectively direct a prescribed volume of reactivegas traversing through the reactive gas conduit 314 to the upstreamsampling module 332 via the sampling conduit 330. Optionally, thesampling control valve 322 may be configured to selectively direct aprescribed flow rate of reactive gas traversing through the reactive gasconduit 314 to the upstream sampling module 332 via the sampling conduit230. Further, any number of additional components, valves, sensors, andthe like may be positioned anywhere along the sampling conduit 330. Forexample, in the illustrated embodiment at least one sensor and/orcontrol device 380 may be positioned along the sampling conduit 330.Exemplary sensor devices include, without limitations, thermocouples,temperature sensors, vacuum gauges, and the like. For example, in oneembodiment the sensor device 380 comprises at least one thermistor. Inanother embodiment the sensor device 380 comprises at least onecalorimetry system or device. Optionally, the sensor device 380 maycomprise one or more titration systems or devices. Those skilled in theart will appreciate the sensor device 380 may comprise any number of insitu measuring devices or systems, flow valves, flowmeters, flowverifiers, and the like.

Referring again to FIG. 4, at least one chamber sampling module 342 maybe in fluid communication with the processing chamber 316 via at leastone chamber sample gas conduit 340. As such, the chamber sampling module342 may be configured to analyze the radical gas stream within theprocessing chamber 316. Like the upstream sampling conduit 330, thechamber sample gas conduit 340 may include one or more valves, sensors,and the like thereon. As such, the flow of sample gas from theprocessing chamber 316 to the chamber sampling module 342 may beselectively varied.

As shown in FIG. 4, optionally, at least one exhaust sampling module 352may be in fluid communication with the processing chamber 316 via atleast one exhaust sample gas conduit 350. As such, the chamber samplingmodule 352 may be configured to analyze the radical gas stream emittedfrom the processing chamber 316 via the exhaust conduit 318. Optionally,the exhaust sample gas conduit 350 may include one or more valves,sensors, and the like thereon. As such, the flow of sample gas emittedfrom the processing chamber 316 via the exhaust conduit 318 may beselectively varied.

With reference to FIG. 4, at least one of the upstream sampling module332, chamber sampling module 342, and exhaust sampling module 352 may becoupled to at least one molecular compound stream conduit 334. Like thesampling conduit 330 the molecular compound stream conduit 334 may bemanufactured from any variety of materials including, withoutlimitation, graphite, silica, carbon fiber, silicon dioxide, silica andcarbide, carbon-based materials, silica-based materials, stainlesssteel, alloys, aluminum, brass, ceramics materials, glass, polymers,plastics, and the like. In one embodiment, at least a portion of atleast one of the upstream sampling conduit 330, chamber sampling module340, exhaust sampling module 350, and/or the molecular compound streamconduit 334 may be configured to react with the radical gas streamflowing therein. For example, in one embodiment at least a portion ofthe sampling conduit 330 and/or molecular compound stream conduit 334may be configured to react with radicals within the gas flow to formchemical species more stable and capable of accurate measurement ascompared to the radicals contained within the radical gas stream.

As shown in FIG. 4, like the previous embodiment at least one sensormodule 336 is in fluid communication with at least one of the upstreamsampling module 332, chamber sampling module 342, and exhaust samplingmodule 352 via the molecular compound stream conduit 334. The sensormodule 336 may be configured to detect and measure the concentration ofradicals in at least one gas flow. Any variety of devices or systems maybe used within or to form the sensor module 336. For example, in oneembodiment the sensor module 336 comprises at least one detectorconfigured to measure the radical flux within the radical gas stream. Inanother embodiment, the sensor module 336 is configured to measure theconcentration of at least one chemical species within a gas flow. Forexample, the sensor module 336 may be configured to measure theconcentration for carbon monoxide (CO), carbon dioxide (CO₂),carbon-hydrogen molecules (methylidyne radical), methylene (CH₂),methyl-group compounds (CH₃), methane (CH₄), silicon tetrafluoride, andsimilar compounds. In one specific embodiment the sensor module 336includes at least one optical gas imaging camera or device such asFourier Transform Infrared spectroscopy system (hereinafter FTIRsystem), tunable filter spectroscopy system (hereinafter TFS system),mass spectrography, optical absorption spectroscopy and the like.Optionally, the sensing module 336 may further include at least onetitration system or device. In one embodiment, the sensing module 336may be configured to reduce or eliminate recombination of the radicalswithin the gas stream into its molecular species. In another embodiment,the sensor module 336 may be configured to permit recombination of theradicals within a gas stream to its molecular species.

Referring again to FIG. 4, at least one sensor module output conduit 362is in fluid communication with the sensor module 336 and the flowmeasurement and/or flow control module 370, which may be configured toaccurately measure a portion of the gas stream flowing there through.Like the previous embodiment, the flow of the gas stream may be measuredusing a mass flow verifier (hereinafter MFV). In another embodiment, theflow of the gas stream may be measured using a mass flow meter(hereinafter MFM). Optionally, the flow may be determined by measuringthe pressure differential between an orifice of known size within themulti-sensor gas sampling detection system 310 with the fluidconductance. Those skilled in the art will appreciate that any varietyof flow measuring devices or systems may be used with the gas samplingdetection system 310 disclosed herein. As shown in FIG. 4, at least oneexhaust conduit 372 may be coupled to or in communication with the flowmeasurement module 370 and configured to exhaust the radical gas streamfrom the gas sampling detection system 310. Optionally, the exhaustconduit 372 may be in fluid communication with at least one vacuumsource (not shown).

The processing system 310 may include at least one optional processormodule 382 in communication with at least one component of theprocessing system 310. For example, the optional processor module 382may be in communication with the radical gas generator 312 via at leastone processor conduit 384. Further, the optional processor system 382may be in communication with at least one of the optional sensor 380 andupstream sampling module 332 via the processor conduit 384 and at leastone optional sensor conduit 356, the sensor module 336 via at least onesensor module conduit 386, or both. As such, the optional processormodule 382 may be configured to measure the flow conditions within theprocessing system 310 and selectively vary the operating conditions ofthe processing system 310 to optimize system performance. Morespecifically, the optional processor module 382 may be configured tomeasure and/or calculate the concentration of radicals within the gasstream and vary the operating characteristics of the radical gasgenerator 312 to increase or decrease the concentration of radicalswithin the radical gas stream. Further, the optional processor module382 may be in communication with and provide/receive data from at leastone of the optional valve device 322, sensor 324, and chamber processormodule 320 via at least one optional processing conduit 364.

FIG. 5 shows schematically an embodiment of a gas sampling detectionsystem useful for detecting the concentration of radicals within a gasstream. As shown, the gas sampling detection system 410 includes atleast one plasma generator and/or radical gas generator 412 in fluidcommunication with at least one processing chamber 416 via at least onegas passage 414. In one embodiment, the radical gas generator 412 is incommunication with at least one sample gas source and at least oneplasma source configured to energize and dissociate sample gases andgenerate at least one reactive gas stream. In one specific embodimentthe radical gas generator 412 comprises a RF toroidal plasma source;although those skilled in the art will appreciate that any variety ofplasma sources or radical gas sources may be used with the presentsystems. In one embodiment the radical gas generator 412 uses hydrogen(H₂) plasma to create atomic hydrogen. In another embodiment the radicalgas generator 412 utilizes oxygen (O₂) plasma to create atomic oxygen.Optionally, the radical gas generator 412 may utilize nitrogentrifluoride (NF₃), fluorine (F₂), chlorine (Cl₂) or any variety of othermaterials to create a reactive plasma containing one or more radicalswithin the gas stream. Alternatively, radical gases may be generated byother gas excitation methods, including electron beam excitation, laserexcitation, or hot-filament excitation. Further, the above descriptiondiscloses various embodiments of RF-based plasma generation systems;although those skilled in the art will appreciate that any variety ofalternate radical gas generation systems may be used with the presentsystem. Exemplary alternate radical gas generation systems include,without limitation, glow discharge plasma systems, capacitively coupledplasma systems, cascade art plasma systems, inductively coupled plasmasystems, wave heated plasma systems, arc discharge plasma systems,coronal discharge plasma systems, dielectric barrier discharge systems,capacitive discharge systems, Piezoelectric direct discharge plasmasystems, and the like.

Referring again to FIG. 5, at least one processing chamber 416 may be influid communication with the radical gas generator 412 via at least onereactive gas conduit 414. In some applications, the reactive gas conduit414 is manufactured from a chemically inert material or a materialhaving low chemical reactivity. Exemplary materials include, withoutlimitation, quartz, sapphire, stainless steel, strengthened steel,aluminum, ceramic materials, glass, brass, nickel, Y₂O₃, YAlO_(x),various alloys, and coated metal such as anodized aluminum. In oneembodiment, a single reactive gas conduit 414 is in fluid communicationwith a single radical gas generator 412. In another embodiment multiplereactive gas conduits 414 are in fluid communication with a singlereactive gas generator 412. In yet another embodiment a single reactivegas conduit 414 is in communication with multiple radical gas generators412. As such, any number of reactive gas conduits 414 may be incommunication with any number of radical gas generators 412. Optionally,the reactive gas conduit 414 may include one or more valve devices orsystems, sensors, or similar devices 422 coupled thereto or incommunication there with. For example, one or more valve devices 422 maybe coupled to the reactive gas conduit 414 thereby permitting a user toselectively permit and/or restrict the flow of at least one reactive gasstream through the reactive gas conduit 414.

The processing chamber 416 may be coupled to or in communication withthe radical gas generator 412 via the reactive gas conduit 414. In oneembodiment, the processing chamber 416 comprises one or more vacuumchambers or vessels configured to have one or more substrates,semiconductor wafers, or similar materials positioned therein.Optionally, the processing chamber 416 may be used for atomic layerprocessing of semiconductor substrates or wafers. Optionally, theprocessing chamber 416 may be used for processing any variety ofsubstrates or materials using any variety of processing methods weresystems. Exemplary processing methods include, without limitation,physical vapor deposition (PVD), chemical vapor deposition (CVD), rapidthermal chemical vapor deposition (RTCVD), atomic layer deposition(ALD), atomic layer etching (ALE), and the like. Those skilled in theart will appreciate that the processing chamber 416 be manufactured fromany variety of materials, including, without limitation, stainlesssteel, aluminum, mild steel, brass, high-density ceramics, glass,acrylic, and the like. In one embodiment, at least one interior surfaceof the processing chamber 416 may include at least one coating, anodizedmaterial, sacrificial material, physical feature or element, and thelike intended to selectively vary the reactivity, durability, and/orfill micro-pores of the interior surfaces of the processing chamber 416.At least one exhaust conduit 418 may be coupled to the processingchamber 416 and configured to evacuate one or more gases or materialsfrom the processing chamber 416. Optionally, one or more controlsensors, valves, scrubbers, or similar devices 424 may be coupled to orpositioned proximate to the exhaust conduit 418, thereby permitting theuser to selectively evacuate one or more gases or other materials fromthe processing chamber 416.

Referring again to FIG. 5, at least one chamber processor module 420 maybe coupled to or otherwise in communication with the processing chamber418 and/or various components of the processing system. The chamberprocessing module 420 may be configured to provide localized control ofthe various components forming the processing system 10. In theillustrated embodiment the chamber processing module 420 is incommunication with the processing chamber 416 via a conduit, althoughthose skilled in your will appreciate that the chamber processing module420 may communicate with any of the components forming the processingsystem 410 via conduit, wirelessly, or both.

As shown in FIG. 5, at least one sampling module 432 may be in fluidcommunication with the radical gas generator 412 via at least onesampling conduit 430. Those skilled in the art will appreciate that thesampling conduit 430 may be manufactured from any variety of materialsincluding, without limitations, stainless steel, alloys, aluminum,brass, ceramics materials, glass, polymers, plastics, carbon fibercarbon-based materials, graphite, silicon, silicon dioxide, siliconcarbide, and the like. As such, in some embodiments the sampling conduit430 may be configured to chemically react with the highly reactiveradicals contained within the radical gas stream flowing therein. In yetanother embodiment, the sampling conduit 430 may consist of a catalyticmaterial to facilitate the recombination of atomic gas species into itsmolecular gas species, such that the recombination energy of the atomicgas is released and measured. In other embodiments, the sampling conduit430 may be configured to be chemically inert.

Referring again to FIG. 5, at least one reaction gas feed or source 472may be configured to provide at least one reaction mechanism or stream474 to the sampling module 432. Alternatively, the reaction source 472may be in communication with the radical gas generator 412 through atleast one stream conduit 475. Any variety of reaction sources 472configured to provide any variety of may be used in the present system.For example, in one embodiment, the reaction source 472 comprises atleast one source of a reactive gas and is configured to react with theatomic radicals, molecular radicals, and short-lived molecules withinthe sampling module 432. Exemplary reactive gases include, withoutlimitations, gases such as nitrogen, oxygen, hydrogen, compounds, suchas NH₃NO₂, or any variety of atomic radicals generated with a separateplasma source. In another embodiment, the reaction source 472 comprisesat least one excitation source configured to provide excitation energyto the atomic radicals, molecular radicals, and short-lived moleculeswithin the sampling module 432. For example, in one embodiment, thereaction source 472 comprises at least one source of optical radiationconfigured to provide excitation energy to the sampling module 432.

As shown in FIG. 5, the sampling conduit 430 may include any variety ofsensors, valves, heating elements, cooling elements, and the likethereon. In one embodiment, the sampling conduit 430 is coupled directlyto and in fluid communication with the radical gas generator 412. In theillustrated embodiment the sampling conduit 430 is in fluidcommunication with the radical gas generator 412 via the reactive gasconduit 414. Optionally, the sampling conduit 430 may be in fluidcommunication with the sampling control valve 422 positioned on thereactive gas conduit 414. For example, the sampling control valve 422may be configured to selectively direct a prescribed volume of reactivegas traversing through the reactive gas conduit 414 to the samplingmodule 432 via the sampling conduit 430. In another embodiment, thesampling control valve 422 may be configured to selectively direct aprescribed flow rate of reactive gas traversing through the reactive gasconduit 414 to the sampling module 432 via the sampling conduit 430.Further, any number of additional components, valves, sensors, and thelike may be positioned anywhere along the sampling conduit 430. Forexample, in the illustrated embodiment at least one sensor and/orcontrol device 450 may be positioned along the sampling conduit 430.Exemplary sensor devices include, without limitations, thermocouples,temperature sensors, optical sensors, UV, optical or infraredspectrometers, charge particle detectors, vacuum gauges, massspectrometers, and the like. For example, in one embodiment the sensordevice 450 comprises at least one thermistor. In another embodiment thesensor device 450 comprises at least one calorimetry system or device.In another embodiment, a novel calorimetry system is discussed in detailand shown in FIGS. 8-15 of the present application. Optionally, thesensor device 450 may comprise one or more titration systems or devices.Those skilled in the arts will appreciate the sensor device 450 maycomprise any number of in situ measuring devices were systems, flowvalves, flowmeters, flow verifiers, and the like.

Referring again to FIG. 5, in the illustrated embodiment the samplingmodule 432 is coupled to at least one molecular compound stream conduit434. Like the sampling conduit 430, the molecular compound streamconduit 434 may be manufactured from any variety of materials including,without limitation, graphite, silica, carbon fiber, silicon dioxide,silica and carbide, carbon-based materials, silica-based materials,stainless steel, alloys, aluminum, brass, ceramics materials, glass,polymers, plastics, and the like. In one embodiment, at least a portionof at least one of the sampling conduit 430 and/or the molecularcompound stream conduit 434 may be configured to react with the radicalgas stream flowing therein. For example, in one embodiment, at least aportion of the sampling conduit 430 and/or molecular compound streamconduit 434 may be configured to react with radicals within the gas flowto form chemical species more stable and capable of accurate measurementas compared to the radicals.

As shown in FIG. 5, at least one sensor module 436 is in fluidcommunication with the sampling module 432 via at least one molecularcompound stream conduit 434. In one embodiment, the sensor module 436may be configured to detect and measure the concentration of radicals inat least one gas flow. Any variety of devices or systems may be usedwithin or to form the sensor module 436. For example, in one embodiment,the sensor module 436 comprises at least one detector configured tomeasure the radical flux within the radical gas stream. In anotherembodiment, the sensor module 436 is configured to measure theconcentration of at least one chemical species within a gas flow. Forexample, the sensor module 436 may be configured to measure theconcentration for carbon monoxide (CO), carbon dioxide (CO₂),carbon-hydrogen molecules (methylidyne radical), methylene (CH₂),methyl-group compounds (CH₃), methane (CH₄), silicon tetrafluoride, andsimilar compounds. In one specific embodiment, the sensor moduleincludes at least one optical gas imaging camera or device such asFourier Transform Infrared spectroscopy system (hereinafter FTIRsystem), tunable filter spectroscopy system (hereinafter TFS system),mass spectrography, optical absorption spectroscopy and the like.Optionally, the sensing module 436 may further include at least onetitration system or device. In one embodiment, the sensing module 436may be configured to reduce or eliminate recombination of the radicalswithin the gas stream into its molecular species. In another embodiment,the sensor module 436 may be configured to permit recombination of theradicals within a gas stream to its molecular species.

Referring again to FIG. 5, at least one sensor module output conduit 438is in fluid communication with the sensor module 436 and the flowmeasurement and/or flow control module 440. In some embodiments, theflow measurement module 440 is configured to accurately measure aportion of the gas stream flowing there through. For example, the flowof the gas stream may be measured using a mass flow verifier (MFV). Inanother embodiment, the flow of the gas stream may be measured using amass flow meter (MFM). Optionally, the flow may be determined bymeasuring the pressure differential between an orifice of known sizewithin the multi-sensor gas sampling detection system 410 with the fluidconductance. Those skilled in the art will appreciate that any varietyof flow measuring devices or systems may be used with the gas samplingdetection system 410 disclosed herein. As shown in FIG. 5, at least oneexhaust conduit 442 may be coupled to or in communication with the flowmeasurement module 440 and configured to exhaust the radical gas streamfrom the gas sampling detection system 410. Optionally, the exhaustconduit 442 may be in fluid communication with at least one vacuumsource (not shown).

As shown in FIG. 5, the processing system 410 may include at least oneoptional processor module 452 in communication with at least onecomponent of the processing system 410. For example, in the illustratedembodiment, an optional processor module 452 is in communication withthe radical gas generator 412 via at least one processor conduit 454.Further, the optional processor system 452 may be in communication withat least one of the optional sensor 450 via the processor conduit 454and at least one optional sensor conduit 456, the sampling module 432via the processor conduit 454 and at least one sampling conduit 458, thesensor module 436 via at least one sensor module conduit 460, and theflow measurement module 440 via at least one flow measurement conduit462. Further, the reaction source 472 may be in communication with theoptional processor system 452 via the processor conduit 454. In oneembodiment, the optional processor module 452 may be configured toprovide and receive data from at least one of the radical gas generator412, the optional sensor 450, the sampling module 432, the sensor module436, and the flow measurement module 440. As such, the optionalprocessor module 452 may be configured to measure the flow conditionswithin the processing system 410 and selectively vary the operatingconditions of the processing system 410 to optimize system performance.More specifically, the optional processor module 452 may be configuredto measure the concentration of radicals within the gas stream vary theoperating characteristics of the radical gas generator 412 to increaseor decrease the concentration of radicals within the radical gas stream.Further, the optional processor module 452 may be in communication withand provide/receive data from at least one of the optional valve device422, sensor 424, and chamber processor module 420 via at least oneoptional processing conduit 464. Optionally, the processor 452 may be incommunication with the various components of the processing system 410wirelessly. Further, the processor 452 may be configured to storeperformance data, processing formulas and times, lot number, and thelike. In addition, the processor 452 may be configured to communicatewith one or more external processors via at least one computer network.

Optionally, as shown in FIG. 5, at least one analysis system or circuit466 may be formed within the processing system 410. As shown, theanalysis system 466 may include at least one of the sampling module 432,sensor module 436, flow measurement module 449, optional sensor 450,optional processor module 452, and the like. Further, the analysissystem 466 may further include valve device 422 or other devices andcomponents within the processing system 410.

FIG. 6 shows schematically an embodiment of a gas sampling detectionsystem useful for detecting the concentration of radicals within a gasstream. As shown, the gas sampling detection system 510 includes atleast one plasma generator and/or radical gas generator 512 in fluidcommunication with at least one processing chamber 516 via at least onegas passage 514. In one embodiment, the radical gas generator 512 is incommunication with at least one sample gas source and at least oneplasma source configured to energize and dissociate sample gases andgenerate at least one reactive gas stream. In one specific embodimentthe radical gas generator 512 comprises a RF toroidal plasma source;although those skilled in the art will appreciate that any variety ofplasma sources or radical gas sources may be used with the presentsystems. In one embodiment the radical gas generator 512 uses hydrogen(H₂) plasma to create atomic hydrogen. In another embodiment the radicalgas generator 512 utilizes oxygen (O₂) plasma to create atomic oxygen.Optionally, the radical gas generator 512 may utilize nitrogentrifluoride (NF₃), fluorine (F₂), chlorine (Cl₂) or any variety of othermaterials to create a reactive plasma containing one or more radicalswithin the gas stream. Alternatively, radical gases may be generated byother gas excitation methods, including electron beam excitation, laserexcitation, or hot-filament excitation. Further, the above descriptiondiscloses various embodiments of RF-based plasma generation systems;although those skilled in the art will appreciate that any variety ofalternate radical gas generation systems may be used with the presentsystem. Exemplary alternate radical gas generation systems include,without limitation, glow discharge plasma systems, capacitively coupledplasma systems, cascade art plasma systems, inductively coupled plasmasystems, wave heated plasma systems, arc discharge plasma systems,coronal discharge plasma systems, dielectric barrier discharge systems,capacitive discharge systems, Piezoelectric direct discharge plasmasystems, and the like.

Referring again to FIG. 6, at least one processing chamber 516 may be influid communication with the radical gas generator 512 via at least onereactive gas conduit 514. In some applications, the reactive gas conduit514 is manufactured from a chemically inert material or a materialhaving low chemical reactivity. Exemplary materials include, withoutlimitation, quartz, sapphire, stainless steel, strengthened steel,aluminum, ceramic materials, glass, brass, nickel, Y₂O₃, YAlO_(x),various alloys, and coated metal such as anodized aluminum. In oneembodiment, a single reactive gas conduit 514 is in fluid communicationwith a single radical gas generator 512. In another embodiment multiplereactive gas conduits 514 are in fluid communication with a singlereactive gas generator 512. In yet another embodiment a single reactivegas conduit 514 is in communication with multiple radical gas generators512. As such, any number of reactive gas conduits 514 may be incommunication with any number of radical gas generators 512. Optionally,the reactive gas conduit 514 may include one or more valve devices orsystems, sensors, or similar devices 522 coupled thereto or incommunication there with. For example, one or more valve devices 522 maybe coupled to the reactive gas conduit 514 thereby permitting a user toselectively permit and/or restrict the flow of at least one reactive gasstream through the reactive gas conduit 514.

As shown in FIG. 6, the processing chamber 516 may be coupled to or incommunication with the radical gas generator 512 via the reactive gasconduit 514. In one embodiment, the processing chamber 516 comprises oneor more vacuum chambers or vessels configured to have one or moresubstrates, semiconductor wafers, or similar materials positionedtherein. For example, the processing chamber 516 may be used for atomiclayer processing of semiconductor substrates or wafers. Optionally, theprocessing chamber 516 may be used for processing any variety ofsubstrates or materials using any variety of processing methods weresystems. Exemplary processing methods include, without limitation,physical vapor deposition (PVD), chemical vapor deposition (CVD), rapidthermal chemical vapor deposition (RTCVD), atomic layer deposition(ALD), atomic layer etching (ALE), and the like. Those skilled in theart will appreciate that the processing chamber 516 may be manufacturedfrom any variety of materials, including, without limitation, stainlesssteel, aluminum, mild steel, brass, high-density ceramics, glass,acrylic, and the like. For example, at least one interior surface of theprocessing chamber 516 may include at least one coating, anodizedmaterial, sacrificial material, physical feature or element, and thelike intended to selectively vary the reactivity, durability, and/orfill micro-pores of the interior surfaces of the processing chamber 16.At least one exhaust conduit 518 may be coupled to the processingchamber 516 and configured to evacuate one or more gases or materialsfrom the processing chamber 516. Optionally, one or more controlsensors, valves, scrubbers, or similar devices 524 may be coupled to orpositioned proximate to the exhaust conduit 518, thereby permitting theuser to selectively evacuate one or more gases or other materials fromthe processing chamber 516.

Referring again to FIG. 6, at least one chamber processor module 520 maybe coupled to or otherwise in communication with the processing chamber518 and/or various components of the processing system. The chamberprocessing module 520 may be configured to provide localized control ofthe various components forming the processing system 510. In theillustrated embodiment the chamber processing module 520 is incommunication with the processing chamber 516 via a conduit, althoughthose skilled in your will appreciate that the chamber processing module520 may communicate with any of the components forming the processingsystem 510 via conduit, wirelessly, or both.

As shown in FIG. 6, at least one sampling module 532 may be in fluidcommunication with the radical gas generator 512 via at least onesampling conduit 530. Those skilled in the art will appreciate that thesampling conduit 530 may be manufactured from any variety of materialsincluding, without limitations, stainless steel, alloys, aluminum,brass, ceramics materials, glass, polymers, plastics, carbon fibercarbon-based materials, graphite, silicon, silicon dioxide, siliconcarbide, and the like. As such, in some embodiments the sampling conduit530 may be configured to chemically react with the highly reactiveatomic radicals, molecular radicals, and short-lived molecules containedwithin the radical gas stream flowing therein. In yet anotherembodiment, the sampling conduit 530 may consist of a catalytic materialto facilitate the recombination of atomic gas species into its moleculargas species, such that the recombination energy of the atomic gas isreleased and measured. In other embodiments, the sampling conduit 530may be configured to be chemically inert. In yet another embodiment, thesampling conduit 530 may consist of a catalyst material configured tofacilitate the recombination of the radical species into its moleculargas species. Optionally, the sampling conduit 530 may include anyvariety of sensors, valves, heating elements, cooling elements, and thelike thereon. In one embodiment, the sampling conduit 530 is coupleddirectly to and in fluid communication with the radical gas generator512. In the illustrated embodiment the sampling conduit 530 is in fluidcommunication with the radical gas generator 512 via the reactive gasconduit 514. Optionally, the sampling conduit 530 may be in fluidcommunication with the sampling control valve 522 positioned on thereactive gas conduit 514. For example, the sampling control valve 522may be configured to selectively direct a prescribed volume of reactivegas traversing through the reactive gas conduit 514 to the samplingmodule 532 via the sampling conduit 530. In another embodiment, thesampling control valve 522 may be configured to selectively direct aprescribed flow rate of reactive gas traversing through the reactive gasconduit 514 to the sampling module 532 via the sampling conduit 530.Further, any number of additional components, valves, sensors, and thelike may be positioned anywhere along the sampling conduit 530. Forexample, in the illustrated embodiment at least one sensor and/orcontrol device 550 may be positioned along the sampling conduit 530.Exemplary sensor devices include, without limitations, thermocouples,temperature sensors, optical sensors, UV, optical or infraredspectrometers, charge particle detectors, vacuum gauges, massspectrometers, and the like. For example, in one embodiment the sensordevice 550 comprises at least one thermistor. In another embodiment thesensor device 550 comprises at least one calorimetry system or device.An embodiment of a novel calorimetry system is discussed in detail andshown in FIGS. 8-15 of the present application. Optionally, the sensordevice 550 may comprise one or more titration systems or devices. Thoseskilled in the arts will appreciate the sensor device 550 may compriseany number of in situ measuring devices were systems, flow valves,flowmeters, flow verifiers, and the like.

Referring again to FIG. 6, in the illustrated embodiment the samplingmodule 532 is coupled to at least one molecular compound stream conduit534. Like the sampling conduit 530, the molecular compound streamconduit 534 may be manufactured from any variety of materials including,without limitation, graphite, silica, carbon fiber, silicon dioxide,silica and carbide, carbon-based materials, silica-based materials,stainless steel, alloys, aluminum, brass, ceramics materials, glass,polymers, plastics, and the like. One embodiment at least a portion ofat least one of the sampling conduit 530 and/or the molecular compoundstream conduit 534 may be configured to react with the radical gasstream flowing therein. For example, one embodiment at least a portionof the sampling conduit 530 and/or molecular compound stream conduit 534may be configured to react with radicals within the gas flow to formchemical species more stable and capable of accurate measurement ascompared to the radicals.

As shown in FIG. 6, at least one sensor module 536 is in fluidcommunication with the sampling module 532 via at least one molecularcompound stream conduit 534. In one embodiment, the sensor module 536may be configured to detect and measure the concentration of radicals inat least one gas flow. Any variety of devices or systems may be usedwithin or to form the sensor module 536. For example, in one embodimentthe sensor module 536 comprises at least one detector configured tomeasure the radical flux within the radical gas stream. In anotherembodiment, the sensor module 536 is configured to measure theconcentration of at least one chemical species within a gas flow. Forexample, the sensor module 536 may be configured to measure theconcentration for carbon monoxide (CO), carbon dioxide (CO₂),carbon-hydrogen molecules (methylidyne radical), methylene (CH₂),methyl-group compounds (CH₃), methane (CH₄), silicon tetrafluoride, andsimilar compounds. In one specific embodiment, the sensor moduleincludes at least one optical gas imaging camera or device such asFourier Transform Infrared spectroscopy system (hereinafter FTIRsystem), tunable filter spectroscopy system (hereinafter TFS system),mass spectrography, optical absorption spectroscopy and the like.Optionally, the sensing module 536 may further include at least onetitration system or device. In one embodiment, the sensing module 536may be configured to reduce or eliminate recombination of the radicalswithin the gas stream into its molecular species. In another embodiment,the sensor module 536 may be configured to permit recombination of theradicals within a gas stream to its molecular species. At least onesensor module return conduit 535 may be in fluid communication with thesensor module 536 and the processing chamber 520. During use, theradical gas or similar material outputted from the sensing module 535may be selectively directed to the processing chamber 520

As shown in FIG. 6, the processing system 510 may include at least oneoptional processor module 552 in communication with at least onecomponent of the processing system 510. For example, in the illustratedembodiment, an optional processor module 552 is in communication withthe radical gas generator 512 via at least one processor conduit 554.Further, the optional processor system 552 may be in communication withat least one of the optional sensor 550 via the processor conduit 554and at least one optional sensor conduit 556, the sampling module 532via the processor conduit 554 and at least one sampling conduit 558, andthe sensor module 536 via at least one sensor module conduit 560. In oneembodiment, the optional processor module 552 may be configured toprovide and receive data from at least one of the radical gas generator512, the optional sensor 550, the sampling module 532, and the sensormodule 536. As such, the optional processor module 552 may be configuredto measure the flows condition within the processing system 510 andselectively vary the operating conditions of the processing system 510to optimize system performance. More specifically, the optionalprocessor module 552 may be configured to measure the concentration ofradicals and/or short-lived molecules within the radical stream and varythe operating characteristics of the radical generator 52 to increase ordecrease the concentration of radicals within the radical gas stream.Further, the optional processor module 552 may be in communication withand provide/receive data from at least one of the optional valve device522, sensor 524, and chamber processor module 520 via at least oneoptional processing conduit 564. Optionally, the processor 552 may be incommunication with the various components of the processing system 510wirelessly. Further, the processor 552 may be configured to storeperformance data, processing formulas and times, lot number, and thelike. In addition, the processor 552 may be configured to communicatewith one or more external processors via at least one computer network.

Optionally, as shown in FIG. 6, at least one analysis system or circuit566 may be formed within the processing system 510. As shown, theanalysis system 566 may include at least one of the sampling module 532,sensor module 536, optional sensor 550, optional processor module 552,and the like. Further, the analysis system 566 may further include valvedevice 522 or other devices and components within the processing system510.

Like the previous embodiments, FIG. 7 shows schematically an embodimentof a gas sampling detection system useful for detecting theconcentration of radicals within a gas stream. As shown, the gassampling detection system 610 includes at least one plasma generatorand/or radical gas generator 612 in fluid communication with at leastone gas passage 614. In one embodiment, the radical gas generator 612 isin communication with at least one sample gas source and at least oneplasma source configured to energize and dissociate sample gases andgenerate at least one reactive gas stream. In one specific embodimentthe radical gas generator 612 comprises a RF toroidal plasma source;although those skilled in the art will appreciate that any variety ofplasma sources or radical gas sources may be used with the presentsystems. In one embodiment the radical gas generator 612 uses hydrogen(H₂) plasma to create atomic hydrogen. In another embodiment the radicalgas generator 612 utilizes oxygen (O₂) plasma to create atomic oxygen.Optionally, the radical gas generator 612 may utilize nitrogentrifluoride (NF₃), fluorine (F₂), chlorine (Cl₂) or any variety of othermaterials to create a reactive plasma containing one or more radicalswithin the gas stream. Alternatively, radical gases may be generated byother gas excitation methods, including electron beam excitation, laserexcitation, or hot-filament excitation. Further, the above descriptiondiscloses various embodiments of RF-based plasma generation systems;although those skilled in the art will appreciate that any variety ofalternate radical gas generation systems may be used with the presentsystem. Exemplary alternate radical gas generation systems include,without limitation, glow discharge plasma systems, capacitively coupledplasma systems, cascade art plasma systems, inductively coupled plasmasystems, wave heated plasma systems, arc discharge plasma systems,coronal discharge plasma systems, dielectric barrier discharge systems,capacitive discharge systems, Piezoelectric direct discharge plasmasystems, and the like.

Referring again to FIG. 7, at least one reactive gas conduit 614 may bein fluid communication with the radical gas generator 612. In someapplications, the reactive gas conduit 614 is manufactured from achemically inert material or a material having low chemical reactivity.Exemplary materials include, without limitation, quartz, sapphire,stainless steel, strengthened steel, aluminum, ceramic materials, glass,brass, nickel, Y₂O₃, YAlO_(x), various alloys, and coated metal such asanodized aluminum. In one embodiment, a single reactive gas conduit 614is in fluid communication with a single radical gas generator 12. Likethe previous embodiment, any number of reactive gas conduits 614 may bein communication with any number of radical gas generators 612. Further,optionally, the reactive gas conduit 614 may include one or more valvedevices or systems, sensors, or similar devices 622 coupled thereto orin communication there with. For example, one or more valve devices 622may be coupled to the reactive gas conduit 614 thereby permitting a userto selectively permit and/or restrict the flow of at least one reactivegas stream through the reactive gas conduit 614. The reactive gasconduit 614 may be coupled to or otherwise in communication with anyvariety of test systems, vessels, containers, processing fixtures and/orsystems, and the like.

As shown in FIG. 7, at least one sampling module 632 may be in fluidcommunication with the radical gas generator 612 via at least onesampling conduit 630. Those skilled in the art will appreciate that thesampling conduit 630 may be manufactured from any variety of materialsincluding, without limitations, stainless steel, alloys, aluminum,brass, ceramics materials, glass, polymers, plastics, carbon fibercarbon-based materials, graphite, silicon, silicon dioxide, siliconcarbide, and the like. As such, in some embodiments the sampling conduit630 may be configured to chemically react with the highly reactiveatomic radicals, molecular radicals, and short-lived molecules containedwithin the radical gas stream flowing therein. In yet anotherembodiment, the sampling conduit 630 may consist of a catalytic materialto facilitate the recombination of atomic gas species into its moleculargas species, such that the recombination energy of the atomic gas isreleased and measured. In other embodiments, the sampling conduit 630may be configured to be chemically inert. In yet another embodiment, thesampling conduit 630 may consist of a catalyst material configured tofacilitate the recombination of the radical species into its moleculargas species. Optionally, the sampling conduit 30 may include any varietyof sensors, valves, heating elements, cooling elements, and the likethereon. In one embodiment, the sampling conduit 630 is coupled directlyto and in fluid communication with the radical gas generator 612. In theillustrated embodiment the sampling conduit 630 is in fluidcommunication with the radical gas generator 612 via the reactive gasconduit 614. Optionally, the sampling conduit 630 may be in fluidcommunication with the sampling control valve 622 positioned on thereactive gas conduit 614. For example, the sampling control valve 622may be configured to selectively direct a prescribed volume of reactivegas traversing through the reactive gas conduit 614 to the samplingmodule 632 via the sampling conduit 630. In another embodiment, thesampling control valve 622 may be configured to selectively direct aprescribed flow rate of reactive gas traversing through the reactive gasconduit 614 to the sampling module 632 via the sampling conduit 630.Further, any number of additional components, valves, sensors, and thelike may be positioned anywhere along the sampling conduit 630. Forexample, in the illustrated embodiment, at least one sensor and/orcontrol device 650 may be positioned along the sampling conduit 630.Exemplary sensor devices include, without limitations, thermocouples,temperature sensors, optical sensors, UV, optical or infraredspectrometers, charge particle detectors, vacuum gauges, massspectrometers, and the like. For example, in one embodiment, the sensordevice 650 comprises at least one thermistor. In another embodiment, thesensor device 650 comprises at least one calorimetry system or device.An embodiment of a novel calorimetry system is discussed in detail andshown in FIGS. 8-15 of the present application. Optionally, the sensordevice 650 may comprise one or more titration systems or devices. Thoseskilled in the art will appreciate the sensor device 650 may compriseany number of in situ measuring devices were systems, flow valves,flowmeters, flow verifiers, and the like.

Referring again to FIG. 7, in the illustrated embodiment the samplingmodule 632 is coupled to at least one molecular compound stream conduit634. Like the sampling conduit 630 the molecular compound stream conduit634 may be manufactured from any variety of materials including, withoutlimitation, graphite, silica, carbon fiber, silicon dioxide, silica andcarbide, carbon-based materials, silica-based materials, stainlesssteel, alloys, aluminum, brass, ceramics materials, glass, polymers,plastics, and the like. One embodiment at least a portion of at leastone of the sampling conduit 630 and/or the molecular compound streamconduit 634 may be configured to react with the radical gas streamflowing therein. For example, one embodiment at least a portion of thesampling conduit 630 and/or molecular compound stream conduit 634 may beconfigured to react with radicals within the gas flow to form chemicalspecies more stable and capable of accurate measurement as compared tothe radicals.

As shown in FIG. 7, at least one sensor module 636 is in fluidcommunication with the sampling module 632 via molecular compound streamconduit 634. In one embodiment, the sensor module 636 may be configuredto detect and measure the concentration of radicals in at least one gasflow. Any variety of devices or systems may be used within or to formthe sensor module 636. For example, in one embodiment the sensor module636 comprises at least one detector configured to measure the radicalflux within the radical gas stream. In another embodiment, the sensormodule 636 is configured to measure the concentration of at least onechemical species within a gas flow. For example, the sensor module 636may be configured to measure the concentration for carbon monoxide (CO),carbon dioxide (CO₂), carbon-hydrogen molecules (methylidyne radical),methylene (CH₂), methyl-group compounds (CH₃), methane (CH₄), silicontetrafluoride, and similar compounds. In one specific embodiment thesensor module includes at least one optical gas imaging camera or devicesuch as Fourier Transform Infrared spectroscopy system (hereinafter FTIRsystem), tunable filter spectroscopy system (hereinafter TFS system),mass spectrography, optical absorption spectroscopy and the like.Optionally, the sensing module 636 may further include at least onetitration system or device. In one embodiment, the sensing module 636may be configured to reduce or eliminate recombination of the radicalswithin the gas stream into its molecular species. In another embodimentthe sensor module 636 may be configured to permit recombination of theradicals within a gas stream to its molecular species.

Referring again to FIG. 7, at least one sensor module output conduit 638is in fluid communication with the sensor module 636 and the flowmeasurement and/or flow control module 640. In some embodiments, theflow measurement module 640 is configured to accurately measure aportion of the gas stream flowing there through. For example, the flowof the gas stream may be measured using a mass flow verifier (MFV). Inanother embodiment, the flow of the gas stream may be measured using amass flow meter (MFM). Optionally, the flow may be determined bymeasuring the pressure differential between an orifice of known sizewithin the multi-sensor gas sampling detection system 610 with the fluidconductance. Those skilled in the art will appreciate that any varietyof flow measuring devices or systems may be used with the gas samplingdetection system 610 disclosed herein. As shown in FIG. 7, at least oneexhaust conduit 642 may be coupled to or in communication with the flowmeasurement module 640 and configured to exhaust the radical gas streamfrom the gas sampling detection system 610. Optionally, the exhaustconduit 642 may be in fluid communication with at least one vacuumsource (not shown).

As shown in FIG. 7, the processing system 610 may include at least oneoptional processor module 652 which may be in communication with atleast one component of the processing system 610. For example, in theillustrated embodiment, an optional processor module 652 is incommunication with the radical gas generator 612 via at least oneprocessor conduit 654. Further, the optional processor system 652 may bein communication with at least one of the optional sensor 650 via theprocessor conduit 654 and at least one optional sensor conduit 656, thesampling module 632 via the processor conduit 654 and at least onesampling conduit 658, the sensor module 636 via at least one sensormodule conduit 660, and the flow measurement module 640 via at least oneflow measurement conduit 662. In one embodiment, the optional processormodule 652 may be configured to provide and receive data from at leastone of the radical gas generator 612, the optional sensor 650, thesampling module 632, the sensor module 636, and the flow measurementmodule 640. As such, the optional processor module 652 may be configuredto measure the flow conditions within the processing system 610 andselectively vary the operating conditions of the processing system 610to optimize system performance. More specifically, the optionalprocessor module 652 may be configured to measure the concentration ofradicals within the gas stream vary the operating characteristics of theradical gas generator 612 to increase or decrease the concentration ofradicals within the radical gas stream. Further, the optional processormodule 652 may be in communication with and provide/receive data from atleast one of the optional valve device 622, and sensor 624. Optionally,the processor 652 may be in communication with the various components ofthe processing system 610 wirelessly. Further, the processor 652 may beconfigured to store performance data, processing formulas and times, lotnumber, and the like. In addition, the processor 652 may be configuredto communicate with one or more external processors via at least onecomputer network.

Optionally, as shown in FIG. 7, at least one analysis system or circuit666 may be formed within the processing system 610. As shown, theanalysis system 666 may include at least one of the sampling module 632,sensor module 636, flow measurement module 649, optional sensor 650,optional processor module 652, and the like. Further, the analysissystem 666 may further include valve device 622 or other devices andcomponents within the processing system 610.

As stated above, the various embodiments of the processing systemdisclosed in FIGS. 1-7 include at least one sampling module and at leastone sensor module. Optionally, as shown in FIGS. 1-7, portions of thesampling module and sensor module may be combined in a single unit ordevice. For example, as shown in FIG. 1 the sampling module 32 andsensor module 36 may be combined in at least one sampling reactionmodule 700. FIGS. 1-7 show various embodiments of processing systemshaving at least one sampling reaction module 700 therein. In theillustrated embodiments the sampling modules and sensor modules areincluded within the sampling reaction module 700. Optionally, portionsof the sampling modules and portions of the sensor modules may beincluded within the sampling reaction module 700. FIGS. 8 and 9 showvarious views of an embodiment of a sampling reaction module 700configured for use with the processing systems disclosed herein, whileFIGS. 10-15 show various views of the components forming the samplingreaction module 700. Further, those skilled in the art will appreciatethat the sampling reaction module 700 may be used in any variety ofsystems. Optionally, the processing systems disclosed herein may beoperated without the inclusion of the sampling reaction module 700.

As shown in FIGS. 8 and 9 the sampling reaction module 700 includes atleast one module body 702 having at least one coupling body 704extending therefrom. At least one coupling body flanged 706 may bepositioned on the coupling body 704. The module body 702 furtherincludes at least one coupling surface 708 having at least one couplingflanged 710 formed thereon. At least one vacuum passage 712 may beformed in the coupling surface 708 proximate to the coupling flanged710. One or more coupling devices 714 may be positioned anywhere on themodule body 702. In one embodiment, the module body 702 is manufacturedfrom stainless steel. In another embodiment the module body 702 ismanufactured from brass. Still another embodiment the module body 702 ismanufactured from copper. Optionally, the module body 702 may bemanufactured from any variety of materials including, withoutlimitations, aluminum alloys, copper alloys, tungsten alloys, tungsten,metallic alloys, ceramics, and similar materials.

Referring again to FIGS. 8 and 9, at least one analysis fixture 720 maybe positioned on or otherwise coupled to the module body 702. At leastone coupling body 740 defining at least one coupling passage 742 mayextend from the module body 702. In the illustrated embodiment at leastone fluid inlet port 760 and at least one fluid outlet port 762 may bepositioned on or otherwise in communication with the analysis fixture720. One or more thermal control modules 750, 752 may be positionedproximate to at least one of the module body 702 in the analysis fixture720. The various features and components of the module body 702 and theanalysis fixture 720 will be described in greater detail in thefollowing paragraphs.

FIGS. 10-13 show various views of the elements forming the analysisfixture 720. As shown, the analysis fixture 720 includes at least oneanalysis fixture body 722 having at least one analysis fixture coverplate 724 position thereon. In the illustrated embodiment the analysisfixture cover plate 724 is selectively detachable from the analysisfixture body 722; although those skilled in the art will appreciate thatthe analysis fixture cover plate 724 need not be separable from theanalysis fixture body 722. The coupling body 740 having at least onecoupling passage 742 included therein may also include at least onecoupling passage support 744 extending from at least one passage mountmounting plate 746. One or more fasteners 748 may traverse through thepassage mounting plate 746 and be configured to couple at least aportion of the analysis fixture 720 to the module body 702 (see FIGS.5-6).

As shown in FIGS. 10-13, one or more thermal control modules 750, 752may be positioned proximate to the analysis fixture 720. In oneembodiment, the thermal control modules 750, 752 comprise thermoelectricmodules configured to regulate the temperature of the sampling tube 780within the analysis fixture 720. In another embodiment, the thermalcontrol modules 750, 752 may comprise at least one thermistor or similardevice. As such, the thermal control modules 750, 752 may include avariety of heating and cooling devices. Optionally, any variety oftemperature regulating devices, fixtures, components, or devices may beused with the analysis fixture 720. In the illustrated embodiment tothermal control modules 750, 752 are used to regulate the temperature ofvarious components of the analysis fixture 720 which in turn mayregulate the temperature of the radical gas stream under analysis. Inone embodiment thermal control modules 750, 752 may be in communicationwith at least one optional processor module used in the processingsystem (see FIGS. 1-7, ref. no. 52, 152, 252, 382, 452, 552, and 652,respectively).

Referring again to FIGS. 10-13, at least one connector relief 754 may beformed in at least one of the analysis fixture body 722 and the analysisfixture cover plate 724. As shown, at least one sampling tube 780 may bepositioned within the coupling body 740. Further, the sampling tube 780may be positioned proximate to the thermal control modules 750, 752. Inone embodiment the sampling tube 780 is manufactured from at least onechemically reactive material. For example, in one embodiment at least aportion of the sampling tube 780 is manufactured from carbon, graphite,silica, carbon fiber, silicon dioxide, silica and carbide, carbon-basedmaterials, silica-based materials, and the like. As such, at least aportion of the sampling tube 780 may be configured to react withradicals contained within the radical gas stream flowing through thesampling tube passage 782 formed within the sampling tube 780, therebyforming chemical species such as carbon monoxide (CO), carbon dioxide(CO₂), carbon-hydrogen molecules (methylidyne radical), methylene (CH₂),methyl-group compounds (CH₃), methane (CH₄), silicon tetrafluoride, andsimilar compounds which may be more easily detected and whoseconcentrations can be easily measured. Optionally, the sampling tube 780may be manufactured from any variety of chemically inert materials suchas stainless steel, ceramics, aluminum, various alloys, and the like.Similarly, the coupling body 740 may be manufactured from any variety ofmaterials. In the illustrated embodiment, the coupling body 740 ismanufactured from a substantially chemically inert material such asstainless steel while sampling tube 780 is manufactured from achemically reactive material such as silicon carbide. As such, thecoupling body 740 may be manufactured from chemically inert orchemically reactive materials.

In one embodiment, the sampling tube 780 is thermally isolated from thesurrounding environment. For example, the sampling tube 780 may bepositioned within the coupling body 740. A vacuum may be maintainedwithin the void between the connection tube 740 and the sampling tube780 thereby thermally isolating the sampling tube 780 from theenvironment. Optionally, the sampling tube 780 may be manufactured inany variety of diameters, lengths, and/or transverse dimensions.

As shown in FIGS. 10-13, one or more seal devices or members may bepositioned on or proximate to sampling passage 780. In the illustratedembodiment, at least one seal device 784 is positioned on the samplingtube 780 and configured to isolate the sampling tube 780 from thecoupling body 740. In one embodiment, the seal device 784 is configuredto minimize the conduction of heat between the connection body 740 andthe sampling tube 780. Further, at least one seal member 786 ispositioned on or near the sampling tube 780 proximate to at least oneplate member 790. In one embodiment, the seal member 786 comprises atleast one crush seal although those skilled in the art will appreciatethe any variety of seal members may be used.

Referring again to FIGS. 10-13, the fluid inlet port 760 and fluidoutlet port 762 may be in communication with one or more fluid portreceivers 764 formed in the analysis fixture body 722. One or more fluidchannels 772 may be in fluid communication with the fluid inlet port 760and the fluid outlet port 762 via the fluid port receivers 764. Duringuse, one or more fluids may be directed through the fluid inlet port760, fluid channel 772, and fluid outlet port 762. As such, variousfluids may be directed through the analysis fixture body 722 toselectively control the temperature of the analysis fixture 720 in theradical gas stream flowing proximate thereto. Further, optionally, atleast one seal member 770 may be positioned proximate to the fluidchannel 772.

As shown in FIGS. 10-13, the plate member 790 may be positionedproximate to the thermal control modules 750, 752. In one embodiment,the plate member 790 is configured to position the thermal controlmodules 750, 752 proximate to the sampling tube 780 and the analysisfixture body 722. In one embodiment, at least one seal body 800 and/orat least one interface seal body 802 may be positioned on or proximateto the plate member 790. As shown, the plate member 790 may include atleast one sampling tube orifice 804 configured to have at least aportion of the sampling tube 780 traverse there through.

FIGS. 14 and 15 show various views of the module body 702 for use withtheir sampling reaction module 700. As shown, the module body 702includes at least one module body face 718. Optionally, at least onefastener receiver may be formed on at least one module body face 718. Inone embodiment, the module body face 718 may be configured to receive atleast one cooling element, body, and/or feature (not shown) thereon orformed therein. For example, in one embodiment cooling elements or finsconfigured to increase the surface area of the module body 702 may beformed on the face of at least one module body face 718. Further, themodule body face 718 may include at least one sampling tube receiver 716configured to receive at least a portion of the sampling tube 780therein (see FIGS. 10-13). As shown in FIG. 12, at least a portion ofthe sampling tube receiver 716 is in fluid communication with at least aportion of the vacuum passage 712 formed in the module body 712. Duringuse, the vacuum passage 712 is coupled to or otherwise in fluidcommunication with a vacuum source (not shown). As such sampling tubereceiver 716 is in fluid communication with the vacuum formed within thevacuum passage 712.

The present application also discloses various methods of measuring theconcentration of radicals in a radical gas stream. FIG. 16 shows ageneral flowchart of the measurement process when used with theprocessing system 10 shown in FIG. 1, although those skilled in the artwill appreciate that the process disclosed herein may be easily adaptedfor use with the various embodiments of the processing systems shown inFIGS. 2-7. As shown, a radical gas stream is created, denoted byreference number 2000 in FIG. 16. Typically, the radical gas stream isgenerated by the radical gas generator 12 shown in FIG. 1. Thereafter, aknown volume and/or flow rate of the radical gas stream is directed toat least one analyzing circuit 66, denoted by reference number 2006 inFIG. 16, while the remaining portion of the radical gas stream isdirected to the processing chamber 16, denoted by reference number 2002,and used to process at least one substrate or otherwise used within theprocessing chamber, denoted by reference number 2004. The known volumeand/or flow rate of radical gas within the analyzing circuit 66 isreacted, denoted by reference number 2008 in FIG. 16, with a reagent tocreate a new, more easy-to-detect/measure chemical species or molecules,or, in the alternative, to recombine back to its molecular species.Exemplary reagents are shown below and include, without limitation: Ni,Al, W, Cu, Co, Zn, C, quartz, alumina, organic carbo-hydrate containingmaterials and various associated oxides, nitrides, and the like.

Optionally, one or more reaction sources 472 may be used to provide oneor more reagents, reactive materials, and/or excitation energy to thesample module 432 to react the radical gas stream to create a new, moreeasy-to-detect/measure chemical species or molecules (See FIG. 5).Typically, the reagent is reacted with the radical gas stream withinproximate to the sampling module 32 to create a compound stream.Thereafter, the compound stream may be directed into the sensor module36 which measures the concentration of the new chemical species ormolecules within the compound stream, denoted by reference number 2010in FIG. 16. Thereafter, the concentration of radicals within theprocessing chamber may be calculated, denoted by reference number 2012in FIG. 16, by comparing the ratio of the concentration of chemicalspecies within the compound stream per defined volume of the radical gasstream forming the sampling gas stream to the remaining volume of the atleast one radical gas stream. Optionally, the optional processor module52 may be configured to receive data sensor module 36 and selectivelyadjust the radical gas generator to optimize the concentration ofradicals within a radical gas stream, denoted by reference number 2014in FIG. 16. Optionally, as shown in FIG. 6, the radical gas stream 535from the sensor module 536 may be directed to the processing chamber520. In another embodiment, those skilled in the art will appreciatethat the measurement systems and methods disclosed herein may be used tomeasure the concentration of atomic radicals, molecular radicals, andother short-lived molecules in any variety of applications. As such, themeasurement systems described herein need not include or be coupled to aprocessing chamber 16 (See FIG. 1). For example, FIG. 7 shows anembodiment of a measurement system 610 wherein the processing chamberhas been eliminated. As such, the measurement systems described hereinmay be used in any variety of application wherein in situ measurement ofatomic radicals, molecular radicals, and/or other short-lived moleculesis desired.

As stated above, the sampling reaction module 700 shown in FIGS. 1-15may be used to determine the concentration of atomic radicals, molecularradicals, short-lived molecules, and other difficult-to-measuremolecules or compounds in situ. In one embodiment, the multi-sensor gassampling detection systems disclosed herein may be configured to usecalorimetry to determine the concentration of molecules or othercompounds within a gas stream wherein the recombination reaction ismeasured using the sampling reaction module 700. FIG. 17 shows a flowchart of one calorimetry-based method utilizing the sampling reactionmodule 700 shown in FIGS. 1 and 8-15. In this embodiment, a flow of aradical gas stream is established within the multi-sensor gas samplingdetection system 10 as a defined flow rate (X sccm), as denoted byreference number 2016. Thereafter, a define flow rate (Y sccm) or volumeof the radical gas stream is directed to the sampling reaction module700 (see reference number 2018 in FIG. 17). The flow of the radical gasstream through the sampling reaction module 700 results in thetemperature of the sampling tube 780 increasing (or decreasing in somecircumstances) in relation to the temperature of the plate member 790(hereinafter dT), which is recorded (see reference number 2020).Further, the rate of temperature variation between the sampling tube 780and the plate member 790 (dT_(m)/dt) is noted (see reference number2022). Thereafter, as denoted as reference number 2024 in FIG. 17, thecalculated sample power may be calculated as follows:Sampled power=C _(p) *m*dT _(m) /dt+P _(loss)(dT)

-   -   Wherein: C_(p=)specific heat capacity        -   m=mass of sampling tube        -   P_(loss)=power loss

As shown in FIG. 17, reference number 2026, the total power may becalculated as follows:Total power=Sampled power*Ysccm/Xsccm

In another embodiment, the multi-sensor gas sampling detection systemsdisclosed herein may be configured to use an alternate calorimetry todetermine the concentration of molecules or other compounds within a gasstream. FIG. 18 shows a flow chart of an alternate calorimetry-basedmethod utilizing a pre-calibrated curve determines the function P_(loss)of components of the sampling reaction module 700 shown in FIGS. 1 and8-15. Like the previous embodiments, a radical gas steam flow isestablished as denoted by reference number 2028. A defined volume, flowrate, or portion of the radical gas steam is directed to at least onesensing unit or device (see reference number 2030). The thermal controlmodule 750 is activated and the time for the sampling tube 780 to reacha stable temperature is observed (see reference number 2032). As such,the recombination reaction is measured at the fixed sampling tubetemperature (U) degrees. In addition, to calculate the sampled power,the mass of the sampling tube 780 is no longer determined by the entiremass of the sampling tube, but rather only a fraction of the mass of thesampling tube 780, denoted as the effective mass m_(eff). As a result,the response time of the sampling reaction module 700 is now faster dueto a smaller thermal mass. The total power may be calculated based onthe sample power.

During use, the sampling tube 780 is heated to a higher temperature (U)(reference number 2032) and then allowed to cool to its steady statetemperature (see reference number 2034). Thereafter, a pre-calibrationcurve may be established based on the observed thermal characteristicsof the sampling reaction module 700. Once the pre-calibration curve hasbeen established a defined flow rate (X sccm) of a radical gas isestablished. A defined flow rate (Y sccm) or volume of radical gas isdirected into the sampling reaction module 700. The thermal controlmodule 750 of the sampling reaction module 700 is set to a prescribedtemperature. Thereafter, the thermal control module 750 is deactivatedand the temperature change to a stable temperature (dT) and rate oftemperature change (dt_(m)) between the sampling tube 780 and the platemember 790 is recorded (reference number 2034).

Thereafter, the calculated sample power may be calculated (referencenumber 2036) as follows:Sampled power=C _(p) *m _(eff) *dT _(m) /dt+P _(loss)(dT)

-   -   Wherein: C_(p)=specific heat capacity        -   m_(eff)=effective mass of sampling tube        -   P_(loss)=power loss

The total power (reference number 2038) may be calculated as follows:Total power=Sampled power*Y sccm/X sccm

FIG. 19 shows a flow chart of another method of utilizing the samplingreaction module 700 shown in FIGS. 1 and 8-15 wherein the recombinationreaction is measured at the fixed sampling tube temperature. In thisembodiment, a flow radical gas stream is established (reference number2040) within the multi-sensor gas sampling detection system 10 as adefined flow rate (X sccm). Thereafter, a defined flow rate (Y sccm) orvolume of the radical gas stream is directed to the sampling reactionmodule 700 (reference number 2042). Thereafter, the temperature of thesampling tube 480 is selectively increased using the thermal controlmodule 750 of the sampling reaction module 700 (reference number 2044).Once the sampling tube 780 reaches a prescribed high temperature(dT_(H)) the thermal control module 750 is deactivated, therebypermitting the sampling tube 780 to return to an equilibrium temperature(reference number 2046). Thereafter, the temperature of the samplingtube 480 is selectively decreased using the thermal control module 750of the sampling reaction module 700 (reference number 2048). Once thesampling tube 780 reaches a prescribed low temperature (dT_(L)) thethermal control module 750 is deactivated, thereby permitting thesampling tube 780 to return to an equilibrium temperature (referencenumber 2050).

Thereafter, the calculated sample high limit power and low limit powermay be calculated (reference number 2052) as follows:Sampled power high limit=P _(loss)(dT _(H))Sampled power low limit=P _(loss)(dT _(L))

-   -   Wherein: P_(loss)=power loss

The upper and lower bound of the reaction may be calculated as follows(reference number 2054):Total power upper bound=Sampled power high limit*Y sccm/X sccmTotal power lower bound=Sampled power low limit*Y sccm/X sccm

The upper and lower bounds determine the error limits of the actualreaction.

FIG. 20 shows graphically an example of the process flow described inFIG. 19 above. As shown, the thermal control module 750, referred to asthe TEC in FIG. 20 is activated to obtain the upper bound of the processand de-activated to obtain the lower bound of the process.

In some instances, determination of the sampled power may requirefurther calibration as distinguishing between the heat generated fromthe radicals recombination as opposed to from the hot gas of the plasmasource is difficult. As such, FIG. 21 shows a calibration processconfigured to distinguishing between the heat generated from theradicals recombination as opposed to from the hot gas of the plasmasource. As shown, a defined flow rate (X sccm) of a radical gas isestablished (reference number 2056). Thereafter, a defined flow rate (Ysccm) or volume of the radical gas stream is directed to the samplingreaction module 700 (reference number 2058). The flow of the radical gasstream through the sampling reaction module 700 results in thetemperature of the sampling tube 780 increasing or decreasing in somecircumstances) in relation to the temperature of the plate member 790(hereinafter dT). The change in temperature of the sampling tube 780 andplate member 790 is recorded (reference number 2060). Further, the rateof temperature variation between the sampling tube 780 and the platemember 790 (dT_(m/dt)) is noted (reference number 2062). Thereafter, thecalculated sample power may be calculated (reference number 2064) asfollows:Sampled power=C _(p) *m*dT _(m) /dt+P _(loss)(dT)

-   -   Wherein: C_(p)=specific heat capacity        -   m=mass of sampling tube        -   P_(loss)=power loss

The total power may be calculated (reference number 2066) as follows:Total power=Sampled power*Y sccm/X sccm

Thereafter, the flow rate (Y′ sccm) or volume of the radical gas streamdirected to the sampling reaction module 700 may be selectively adjusted(reference number 2068). For example, at least one valve device 22 (SeeFIG. 1) may be adjusted to vary the flow of radical gas into thesampling reaction module 700. As shown in FIG. 22, after collecting thesampled power at several different sampling flows, the results can beplotted and used to extrapolate a reading at 0 flow (valve closed). Theslope of the extrapolated line is then the sensitivity of themeasurement to the sampled flow, which will have a greater dependence onthe radicals recombination, and less on the heat from the hot gas.

Optionally, multi-sensor gas detection sampling system 700 may includeat least one optically reactive material and at least one detector suchas an FTIR or TFS thereby using optically-based determination of thesampled power. As such, rather than performing the diagnostics in situwhere it is exposed to the radical elements materials, the user may wishto recombine the radical species into a molecular gas species first,then transport the molecular gas species to the optical sensing device,which may now be located farther away. For example, in one specificexample, a carbon material may be used within the multi-sensor gasdetection sampling system 700. During use, an atomic species such asoxygen react with the carbon and produce CO or CO₂. The CO or CO₂ gasescan then be diverted to a remote optical sensor to detect the amount COor CO₂ present. Thereafter, as shown in FIG. 23, the concentration ofCO, CO₂, can be optically determined, thereby providing theconcentration of O-radicals within the gas stream. The reagent materialmay be chosen such that it only reacts with the atomic species and notwith its molecular species. Exemplary reagent materials include:

Gases that Radical to be cannot be Species to be sensed/reacted Materialfor reaction sensed detected H Carbon (graphite, C- H₂ CH_(x) fiber,a-C), Si, SiO₂ O Carbon(graphite, C- O₂, H₂O CO, CO₂ fiber, a-C) F, ClSilicon, SiO₂, SiC NF₃, F₂, Cl₂ SiF₄

FIG. 24 shows a flow chart of an exemplary optically-based measurementprocess. As shown, the thermal control module 750 of the samplingreaction module 700 is set to a stable desired temperature (U)(reference number 2070). Thereafter, a defined flow rate (X sccm) of aradical gas is established (reference number 2072). Further, a definedflow rate (Y sccm) or volume of the radical gas stream is directed tothe sampling reaction module 700 (reference number 2074). A spectrumfrom the optical sensor or detector (FTIP/TFS) within the thermalcontrol module 750 may be recorded (reference number 2076). Thereafter,the radical output may be calculated (reference number 2078) as follows:Radical output=f(spectrum peak)*X sccm/Y sccm

The flow rate (Y′ sccm) or volume of the radical gas stream directed tothe sampling reaction module 700 may be selectively adjusted (referencenumber 2080). For example, at least one valve device 22 (See FIG. 1) maybe adjusted to vary the flow of radical gas into the sampling reactionmodule 700. As a result, the measured result indicates the relativeamplitude of a given radical stream, which can be used for processmonitoring. Also, the sampling tube 780 may be is set at a fixedtemperature to improve the selectivity of the reaction. For example, atemperature may be chosen so that the reacting material willpreferentially react with the atomic radical species and not themolecular gas species.

In another embodiment, the sampling reaction module 700 may include asemiconductor-based sampling architecture in which at least onesemiconductor material is positioned within the sampling reaction module700. More specifically, as shown in FIG. 25, the thermal control module750 of the sampling reaction module 700 is set to a stable desiredtemperature (U) (reference number 2082). Thereafter, a defined flow rate(X sccm) of a radical gas is established (reference number 2084).Further, a defined flow rate (Y sccm) or volume of the radical gasstream is directed to the sampling reaction module 700 (reference number2086). A resistance from at least one semiconductor sensor positionedwithin the sampling reaction module 700 may be recorded (referencenumber 2088). Thereafter, the radical output may be calculated(reference number 2090) as follows:Radical output=% of change in resistance

FIG. 26 shows graphically the result of resistance change as the radicaloutput stream is activated and deactivated when using theresistance-based sampling architecture described above and shown in FIG.25.

FIG. 6 described above shows schematically embodiment of a gas samplingdetection system useful for detecting the concentration of radicalswithin a gas stream. In contrast to the system described in FIG. 6, FIG.27 shows an embodiment of a gas sampling detection system 910 whichincludes a novel calorimetry architecture positioned downstream of theradical gas generator or remote plasma source. As shown in FIG. 27, thegas sampling detection system 910 includes at least one plasma generatorand/or radical gas generator 912 in fluid communication with at leastone processing chamber 916 via at least one reactive gas conduit 914. Inone embodiment, the radical gas generator 912 is in communication withat least one sample gas source and at least one plasma source configuredto energize and dissociate sample gases and generates at least onereactive gas stream. In one specific embodiment the radical gasgenerator 912 comprises a RF toroidal plasma source; although thoseskilled in the art will appreciate that any variety of plasma sources orradical gas sources may be used with the present systems. In oneembodiment the radical gas generator 912 uses hydrogen (H₂) plasma tocreate atomic hydrogen. In another embodiment the radical gas generator912 utilizes oxygen (O₂) plasma to create atomic oxygen. Optionally, theradical gas generator 912 may utilize nitrogen trifluoride (NF₃),fluorine (F₂), chlorine (Cl₂), ammonia (NH₃) or any variety of othermaterials to create a reactive plasma containing one or more radicalswithin the gas stream. Alternatively, radical gases may be generated byother gas excitation methods, including electron beam excitation, laserexcitation, or hot-filament excitation. Further, the above descriptiondiscloses various embodiments of RF-based plasma generation systems;although those skilled in the art will appreciate that any variety ofalternate radical gas generation systems may be used with the presentsystem. Exemplary alternate radical gas generation systems include,without limitation, glow discharge plasma systems, capacitively coupledplasma systems, cascade arc plasma systems, inductively coupled plasmasystems, wave heated plasma systems, arc discharge plasma systems,coronal discharge plasma systems, dielectric barrier discharge systems,capacitive discharge systems, Piezoelectric direct discharge plasmasystems, and the like.

Referring again to FIG. 27, at least one processing chamber 916 may bein fluid communication with the radical gas generator 912 via at leastone reactive gas conduit 914. In some applications, the reactive gasconduit 914 is manufactured from a chemically inert material or amaterial having low chemical reactivity. Exemplary materials include,without limitation, quartz, sapphire, stainless steel, strengthenedsteel, aluminum, ceramic materials, glass, brass, nickel, Y₂O₃,YAlO_(x), various alloys, and coated metal such as anodized aluminum. Inone embodiment a single reactive gas conduit 914 is in fluidcommunication with a single radical gas generator 912. In anotherembodiment multiple reactive gas conduits 914 are in fluid communicationwith a single radical gas generator 912. In yet another embodiment, asingle reactive gas conduit 914 is in communication with multipleradical gas generators 912. Optionally, the reactive gas conduit 914 maycomprise a sampling conduit or tube performing a similar function to thesampling tube 780 described above and shown in FIGS. 11-13. As such, anynumber of reactive gas conduits 914 may be in communication with anynumber of radical gas generators 912. Further, at least one valve deviceor sensor device 922 may be included on the reactive gas conduit 914between the radical gas generator 912 and the processing chamber 916.For example, in one embodiment the valve device 922 may be configured toselectively permit or restrict the flow of at least one fluid throughthe reactive gas conduit 914 to create a desired pressure differentialbetween the radical gas generator 912 and the processing chamber 916. Inone embodiment, the valve device 922 may comprise a variable valve or,in the alternative, a fixed-sized orifice. In one embodiment, the valvedevice 922 may be positioned downstream of sensor device 950, as shownin FIG. 27. Alternatively, the valve device 922 may be positionedupstream of sensor device 950.

As shown in FIG. 27, the processing chamber 916 may be coupled to or incommunication with the radical gas generator 912 via the reactive gasconduit 914. In one embodiment, the processing chamber 916 comprises oneor more vacuum chambers or vessels configured to have one or moresubstrates, semiconductor wafers, or similar materials positionedtherein. For example, the processing chamber 916 may be used for atomiclayer processing of semiconductor substrates or wafers. Optionally, theprocessing chamber 916 may be used for processing any variety ofsubstrates or materials using any variety of processing methods orsystems. Exemplary processing methods include, without limitation,physical vapor deposition (PVD), chemical vapor deposition (CVD), rapidthermal chemical vapor deposition (RTCVD), atomic layer deposition(ALD), atomic layer etching (ALE), and the like. Those skilled in theart will appreciate that the processing chamber 916 be manufactured fromany variety of materials, including, without limitation, stainlesssteel, aluminum, mild steel, brass, high-density ceramics, glass,acrylic, and the like. For example, at least one interior surface of theprocessing chamber 916 may include at least one coating, anodizedmaterial, sacrificial material, physical feature or element, and thelike intended to selectively vary the reactivity, durability, and/orfill micro-pores of the interior surfaces of the processing chamber 916.At least one exhaust conduit 918 may be coupled to the processingchamber 916 and configured to evacuate one or more gases or materialsfrom the processing chamber 916. Optionally, one or more controlsensors, valves, scrubbers, or similar devices 924 may be coupled to orpositioned proximate to the exhaust conduit 918, thereby permitting theuser to selectively evacuate one or more gases or other materials fromthe processing chamber 916.

Referring again to FIG. 27, at least one chamber processor module 920may be coupled to or otherwise in communication with the processingchamber 916 and/or various components of the processing system. Thechamber processing module 920 may be configured to provide localizedcontrol of the various components forming the processing system 910. Inthe illustrated embodiment the chamber processing module 920 is incommunication with the processing chamber 916 via at least one conduit,although those skilled in your will appreciate that the chamberprocessing module 920 may communicate with any of the components formingthe processing system 910 via conduit, wirelessly, or both.

As shown in FIG. 27, the reactive gas conduit 914 may include one ormore sensor systems and/or similar devices 950 coupled thereto or incommunication there with. For example, in the illustrated embodiment, atleast one calorimetry sensor device 950 may be positioned within and/orcoupled to the reactive gas conduit 914, although those skilled in theart will appreciate any variety of sensor devices or systems may be usedin the present system. Unlike the embodiments shown in FIG. 6 anddescribed above, the embodiment of the gas sampling detection system 910shown in FIG. 27 need not include the embodiment of the sample reactionmodule 700 included in gas sampling detection system 510 shown in FIG.6.

As shown in FIG. 27, the processing system 910 may include at least oneoptional processor module 952 in communication with at least onecomponent of the processing system 910. For example, in the illustratedembodiment, an optional processor module 952 is in communication withthe radical gas generator 912 and power supply 926 via at least oneprocessor conduit 954. Further, the optional processor system 952 may bein communication with the sensor 950 via the processor conduit 954 andthe sensor conduit 958. In one embodiment, the optional processor module952 may be configured to provide and receive data from at least one ofthe radical gas generator 912, the power supply 926 and the sensordevice 950. As such, the optional processor module 952 may be configuredto measure the flow conditions within the processing system 910 via thesensor device 950 and selectively vary the operating conditions of theprocessing system 910 or the power supply 926 to optimize systemperformance. More specifically, the optional processor module 952 may beconfigured to measure the concentration of radicals and/or short-livedmolecules within the radical gas stream and vary the operatingcharacteristics of the radical gas generator 912 to increase or decreasethe concentration of radicals within the radical gas stream. As statedabove, the sensor device 950 may comprise a calorimetry sensor device950. Further, the optional processor module 952 may be in communicationwith and provide/receive data from at least one of the optional valvedevice 922 (via conduit 958) and chamber processor module 920 (viaconduit 964). The optional processor module 952 may also be configuredto provide and receive plasma power or input power to the power supply926. Optionally, the processor 952 may be in communication with thevarious components of the processing system 910 wirelessly. Further, theprocessor 952 may be configured to store performance data, processingformulas and times, lot number, and the like. In addition, the processor952 may be configured to communicate with one or more externalprocessors via at least one computer network.

FIGS. 28 and 29 show various embodiments of a sensor architecture ordevice which may be used to form the sensor device 950. As shown in FIG.28, in one embodiment the sensor device 950 may be coupled to orotherwise in communication with the reactive gas conduit 914 via atleast one conduit 974. Further, at least one sensor body 970 may bepositioned within at least one gas passage 915 formed within thereactive gas conduit 914 and in communication with the sensor device 950via the conduit 974. In the illustrated embodiment, a single sensor body970 is positioned within the reactive gas conduit 914, although thoseskilled in art will appreciate any number of sensor bodies may bepositioned within the reactive gas conduit 914 and coupled to the sensordevice 950. Further, in one embodiment the sensor body 970 is thermallyisolated from the reactive gas conduit 914 using at least one isolationdevice 972. In the alternative, those skilled in the art will appreciatethat the sensor body 970 need not be thermally isolated from thereactive gas conduit 914. The sensor body 970 may be manufactured fromany variety of materials, including, without limitations, carbon,graphite, silica, carbon fiber, silicon dioxide, silica and carbide,carbon-based materials, silica-based materials, and the like. As such,at least a portion of the sensor body 970 may be configured to reactwith radicals contained within the radical gas stream flowing throughthe reactive gas conduit 914, thereby forming chemical species such ascarbon monoxide (CO), carbon dioxide (CO₂), carbon-hydrogen molecules(methylidyne radical), methylene (CH₂), methyl-group compounds (CH₃),methane (CH₄), silicon tetrafluoride, and similar compounds which may bemore easily detected. Optionally, the sensor body 970 may bemanufactured from any variety of chemically inert materials such asstainless steel, ceramics, nickel, tungsten, aluminum, various alloys,and the like. Optionally, the sensor body 970 may also be manufacturedfrom a catalytic material such as platinum, palladium, nickel that mayreact with one or more elements or chemical compounds in the radical gasstream, providing chemical composition and/or concentration of specificgases in the radical gas.

During use, a reactive gas 913 generated by the plasma generator isdirected through the reactive gas conduit 914. The sensor body 970positioned within the gas passage 915 formed in the reactive gas conduit914 is located within the stream of radical gas 913. The temperature ofthe thermally isolated sensor body 970 is measured by the sensor device950. Thereafter, sensor device 950 provides the calorimetric datameasured by the sensor body 970 to at least one of the optionalprocessor module 952 and/or the plasma generator 912. As such, theoperational parameters of the radical gas generator 912 may be adjustedbased on the calorimetric measurements performed by the sensor device950.

FIG. 29 shows another embodiment of a reactive gas conduit 914 having asensor device 950 in communication therewith. More specifically, thesensor device 950 includes a first sensor body 976 and a second sensorbody 978 positioned on or otherwise coupled to at least one thermal body980. As shown in the illustrated embodiment, the first sensor body 976may be positioned within at least one gas passage 915 formed in thereactive gas conduit 914 (and within the radical gas stream 913) whilethe second sensor body 978 is located distally from the reactive gasconduit 914. In an alternate embodiment, the first sensor body 976 andsecond sensor body 978 are both positioned within the proximate to thereactive gas conduit 914. Further, the thermal body 980 may include atleast one fluid inlet 982 and at least one fluid outlet 984. In oneembodiment, the thermal body 980 may be configured to maintain at leasta portion of the reactive gas conduit 914 at a desired temperature. Likethe previous embodiment, at least one of the first sensor body 976and/or the second sensor body 978 is in communication with the sensordevice 950 via at least one conduit 978. During use, the temperature ofthe first sensor body 976 positioned within the gas passage 915 formedwithin the radical gas stream is measured by the sensor device 950 whena reactive gas 913 flows through the reactive gas conduit 914. Inaddition, the temperature of the second sensor body 978 is similarlymeasured by the sensor device 950. Thereafter, the temperature gradientbetween the first sensor body 976 and second sensor body 978 may becalculated by at least one of the sensor device 950 and the optionalprocessor module 952. Thereafter, the performance characteristics of theradical gas generator 912 may be adjusted to optimize performance.Optionally, the temperature of the fluid flowing into the thermal body980 via the fluid inlet 982 may be compared to the temperature of thefluid flowing out of the thermal body 980 via the fluid outlet 984 andfluid outlet 984, thereby permitting a user to calculate heat transferwithin the thermal body 980. In one embodiment, the reactive gas conduit914 may be configured to permit radicals within the gas stream flowingwithin the reactive gas conduit 914 to recombine. As such, those skilledin the art will appreciate that the recombination power of the gasstream (output calorimetry) may be calculated by at least one of thesensor body 950 in the optional processor module 952.

FIG. 30 shows an alternate embodiment of a radical gas conduit 1014 inwhich at least one surface of the reactive gas conduit 1014 forms athermal sensor device. More specifically, the reactive gas conduit 1014includes a conduit body 1016 having at least one inner surface 1018 andat least one outer surface 1019. As such, the inner surface 1016 of thereactive gas conduit 1014 defines at least one gas passage 1015.Further, at least one thermal body 1020 may be coupled to or otherwisein communication with at least a portion of the reactive gas conduit1014. As shown, the thermal body 1020 may include at least one inlet1022 and at least one outlet 1024. The inlet 1022 and outlet 1024 may bein communication with at least one conduit 1026 traversing through orpositioned proximate to the thermal body 1020. In one embodiment, atleast one fluid may be flowed through the thermal body 1020 via theinlet 1022, outlet 1024, and conduit 1026. In the illustratedembodiment, a thermal body 1020 is positioned proximate to a section ofthe reactive gas conduit 1014. Optionally, the thermal body 1020 may bepositioned along the entire length of the reactive gas conduit 1014.

Referring again to FIG. 30, at least one sensor device 1028 may bepositioned within the conduit body 1016 of the reactive gas conduit1014. For example, in the illustrated embodiment, the sensor device 1028is positioned on or proximate to the inner surface 1015 of the conduitbody 1016. In one embodiment, the sensor device 1028 includes at leastone sensor therein. In the illustrated embodiment, the sensor device1028 includes a first sensor region 1030 and at least a second sensorregion or device 1032. In the illustrated embodiment, the first sensor1030 may be located within or proximate to the inner surface 1018 of theconduit body 1016. Optionally, the entire inner surface 1018 may beconfigured to form the first sensor region 1030. As such, the firstsensor region 1030 may be configured to measure recombinationtemperature/energy of the radical flow within the reactive gas conduit1014. The second sensor region 1032 may be positioned external of theconduit body 1016. For example, in one embodiment the second sensorregion 1032 may be positioned proximate to the outer surface 1019 of theconduit body 1016. In one embodiment, the second sensor region 1032 isconfigured to measure temperature external of the conduit body 1016.During use, the user may calculate a temperature gradient between thefirst sensor region 1030 positioned on or proximate to the inner surface1018 within the conduit body 1016 and the second sensor region 1032positioned proximate to the outer surface 1019 external of the conduitbody 1016. Optionally, additional sensor regions 1029 may be positionedon the gas conduit 1014. For example, in the illustrated embodiment anadditional sensor 1029 is positioned proximate to the thermal body 1020.The first and second sensor regions 1030, 1032 may be separated by atleast one thermal region 1034 which is in communication with the thermalbody 1020. Optionally, the thermal region 1034 may include one or moreconduits (not shown) configured to have one or more fluids flowed therethrough. As such, the thermal region 1034 may be in communication withthe inlet 1022 and outlet 1024 formed on the thermal body 1020. Inanother embodiment, the inner surface 1018 of the conduit body 1016 maybe configured to act as a sensor. Like the previous embodiment, thesensor device 1028 may be in communication with at least one sensorcontroller 1040 via at least one sensor conduit 1042.

During use, the temperature of the recombination heat of the reactivegas flow flowing through the reactive gas conduit 1014 is measured bythe sensor device 1028 for sensor region 1030, and the additional sensorregion 1029 for sensor region 1032, which are both in communication withthe sensor device 1040. Thereafter, the performance characteristics ofthe radical gas generator 912 may be adjusted to optimize performance(See FIG. 27). Optionally, the temperature of the fluid flowing into thethermal body 1020 via the fluid inlet 1022 may be compared to thetemperature of the fluid flowing out of the thermal body 1020 via thefluid outlet 1024, thereby permitting a user to calculate heat transferwithin the thermal body 1020. In one embodiment, the reactive gasconduit 1014 may be configured to permit radicals within the gas streamflowing within the reactive gas conduit 1014 to recombine. As such,those skilled in the art will appreciate that the recombination power ofthe gas stream (total output calorimetry) may be calculated by at leastone of the sensor body 1040 in the optional processor module 952 (SeeFIG. 27).

FIG. 31 shows a flow chart of another method of utilizing the samplingreaction module 910 shown in FIGS. 27, 29 and 30. In this embodiment, aflow radical gas stream is established within the multi-sensor gassampling detection system 910 as a defined flow rate (X sccm) (referencenumber 2092). Thereafter, the change in temperatures of the first sensorbody 982 and second sensor body 984 is recorded (reference number 2094).Further, the rate of the temperature change (dT_(m)/dt) of the reactivegas conduit 914 is also recorded (reference number 2096). Thereafter,the sample power may be calculated (reference number 2098) as follows:Sampled power=C _(p) *m _(rgc) *dT _(m) /dt+P _(loss)(dT)

-   -   Wherein: C_(p)=specific heat capacity        -   m_(eff)=effective mass of sampling tube        -   P_(loss)=power loss

FIG. 32 shows another flow chart of an alternate method of utilizing thesampling reaction module 910 shown in FIGS. 27, 29 and 30. In thisembodiment, a flow radical gas stream is established within themulti-sensor gas sampling detection system 910 as a defined flow rate (Xsccm) (reference number 2100). Thereafter, the power delivered to thereactive gas flow may be recorded 2102. In addition, the temperaturerise (dT) and rate of temperature rise (dT_(m)/dT) may be measuredbetween at least two sensors positioned or proximate to the reactive gasconduit 914 (See FIGS. 27, 29, and 30, FIG. 31 reference number 2104).Optionally, the temperature rise (dT) and rate of temperature rise(dT_(m)/dT) may be measured (reference number 2106) between at least twosensors locations formed in the sensor device 1028 shown in FIG. 31.Thereafter, the sample power may be calculated (reference number 2108)as follows:Sampled power=C _(p) *m*dT _(m) /dt+P _(loss)(dT)

-   -   Wherein: C_(p)=specific heat capacity        -   m=mass of sampling tube        -   P_(loss)=power loss

Thereafter, the sample power may be compared (reference number 2110) tothe gas flow rate and power of the reactive gas, thereby allowing theefficiency of the reactive gas generator to be accurately calculated.Further, the output of the radical gas generator 912 may be assessed(reference number 2112) and selectively adjusted (reference number 2114)by the optional processor module 952, the power supply 926, or both.

FIG. 33 shows graphically the temperature change (dT) of the fluid to areactive gas conduit 914 downstream of the radical gas generators 912when the radical gas generators 912 is repeatedly cycled between on andoff. As shown, when the radical gas generator 912 is initially activatedthe temperature of the fluid rises and subsequently drops to a lowervalue during the off cycle. As shown in FIG. 33, with the temperaturechange (dT) far from reaching steady state during each cycle, the slopeof the temperature rise is proportional to the power absorbed by thereactive gas conduit 914 from the radical gas stream generated by theradical gas generators 912.

FIGS. 34A and 34B shows graphically that two different radical gasgenerators may have different radical outputs. More specifically, thedata of radical gas generator unit #1 shown in FIG. 34A has lower slopein temperature rise (dT/dt) compared to the radical generator unit #2shown in FIG. 34B. On the other hand, the power input to radicalgenerator unit #1 is higher than the power to radical gas generator #2.

As shown in FIG. 34A, the input power to radical gas generator unit #1increases from about 7.5 kW to about 10 kW during 300 operation cycles.During the same time, power in the radical gas output decreases. Thereis a rapid drop during the initial few cycles when the surface of theradical gas generator is changed by plasma-surface interactions in theprocess chemistry. Subsequently, there is a slow drop of power in theradical gas output stream while the input plasma power increases. Thisbehavior is quite different from that of radical gas generator unit #2shown in FIG. 34B. Not only the power in the output radical gas steam ishigher by as much as 30-40%, the input power to radical gas generator #2is lower during the entire test. It shows that the radical gas generatorunit #2 is more efficient than unit #1. The higher input power and lowerpower in the output radical gas stream show that there is higher loss ofradical gases in radical gas generator #1, which relates to differencein surface compositions of the two radical gas generators. Therefore,the method of FIG. 32 can not only be used to control or adjust theoperation of a radical gas generator, but may also be used to determineand characterize the performance status of a radical gas generator. Theability of separating a bad or deteriorated radical gas generator fromthe normal ones is particularly useful in an industrial manufacturingenvironment to ensure consistency of the products.

The embodiments disclosed herein are illustrative of the principles ofthe invention. Other modifications may be employed which are within thescope of the invention. Accordingly, the devices disclosed in thepresent application are not limited to that precisely as shown anddescribed herein.

What is claimed is:
 1. A system for measuring the concentration ofradicals in a gas stream, comprising: at least one radical gas generatorin communication with at least one gas source, the radical gas generatorconfigured to generate at least one radical gas stream; at least oneprocessing chamber in fluid communication with the at least one radicalgas generator, the at least one processing chamber configured to receivea portion of the at least one radical gas stream; at least one samplingreaction module in fluid communication with the at least one radical gasgenerator, the sampling reaction module having at least one thermalcontrol module in thermal communication with at least one sampling tube,the at least one sampling tube configured to receive a portion of theradical gas stream from the at least one radical gas generator thereinand react at least one reagent with at least one radical gas within adefined volume of the at least one radical gas stream thereby forming atleast one chemical species within at least one compound stream; at leastone sensor module positioned within the at least one sampling reactionmodule and configured to measure a change of temperature of the at leastone sampling tube due to interaction of the at least one chemicalspecies within the at least one compound stream and the sampling tubeand calculate a concentration of the at least one chemical specieswithin the at least one compound stream flowing within the at least onsampling tube based on the measured temperature change of the at leastone sampling tube; at least one flow measurement module in fluidcommunication with at least one sampling reaction module, the at leastone flow measurement module configured to measure a volume of the atleast one of the at least one radical gas stream and at least onecompound stream; and at least one exhaust conduit configured to exhaustthe at least one radical gas stream from the flow measurement module. 2.The system of claim 1 wherein the at least one reagent comprisescarbon-based materials.
 3. The system of claim 1 wherein the at leastone reagent comprises at least one material selected from the groupconsisting of graphite, silica, carbon fiber, silicon dioxide, andsilicon carbide.
 4. The system of claim 1 wherein the at least onesampling module includes at least one calorimetry measurement system. 5.The system of claim 1 wherein the at least one sensor module comprisesat least one Fourier transform infrared spectroscopy system.
 6. Thesystem of claim 1 wherein at least one flow measurement module includesat least one mass flow verifier.
 7. The system of claim 1 furthercomprising at least one processor in communication with at least one ofthe at least one radical gas generator, at least one sampling module, atleast one sensor module, and at least one flow measurement module, theat least one processor configured to controllably adjust to generationof at least one radical gas stream emitted from the at least one radicalgas generator based on data received from at least one of the at leastone analysis circuit, the at least one sampling module, the at least onesensor module, and the at least one flow measurement module.